Applications of clays in nanocomposites and ceramics

Ci a ion: Kalendo a, A.; Kupko a, J.; U basko a, M.; Me inska, D. Applica ions o Clays in Nanocomposi es and Ce amics. Mine als 2024,14, 93. h ps:// doi.o g/10.3390/min14010093 Academic Edi o : Janos K is o Recei ed: 2 Decembe 2023 Re ised: 7 Janua y 2024 Accep ed: 9 Janua y 2024 Published: 13 Janua y 2024 Copy igh : © 2024 by he au ho s. Licensee MDPI, Basel, Swi ze land. This a icle is an open access a icle dis ibu ed unde he e ms and condi ions o he C ea i e Commons A ibu ion (CC BY) license (h ps:// c ea i ecommons.o g/licenses/by/ 4.0/). mine als Re iew Applica ions o Clays in Nanocomposi es and Ce amics Alena Kalendo a 1,* , Jana Kupko a 2, Ma ina U basko a 1and Dagma Me inska 3 1 Depa men o Polyme Enginee ing, Facul y o Technology, Tomas Ba a Uni e si y in Zlín, Va ecko a 5669, 76001 Zlín, Czech Republic 2Nano echnology Cen e, CEET, VSB-Technical Uni e si y o Os a a, 17. Lis opadu 15, 70833 Os a a, Czech Republic; [email p o ec ed] 3Depa men o P oduc ion Enginee ing, Facul y o Technology, Tomas Ba a Uni e si y in Zlín, Va ecko a 5669, 76001 Zlín, Czech Republic; [email p o ec ed] *Co espondence: [email p o ec ed]; Tel.: +420-739-659-478 Abs ac : Clays and clay mine als a e common na u al ma e ials, he unique p ope ies o which ha e a ac ed he in e es o he indus y, especially because hese ma e ials a e easily a ailable, cheap, and non- oxic. Clays and clay mine als a e widely used in many applica ions, such as in ce amic p oduc- ion, in he cla i ica ion o liquids, pollu an adso be s, ille in composi es and nanocomposi es, soil amendmen s, in pha macy, e c. This e iew assesses he de elopmen in he a ea o clay applica ion in nanocomposi es and ce amics. The i s pa o his s udy co e s polyme /clay nanocomposi es. Topics o in e es include nano ille sou ces o polyme nanocomposi es, he possible ways o clay modi ica ion, polyme /clay nanocomposi e classi ica ion and hei p ocessing, and polyme ma ix o e iew wi h possible enhancemen o nanocomposi e p ope ies. Some o he applica ions ha e al eady been comme cialized. App oxima ely 80% o he polyme /clay nanocomposi es a e des ined o he au omo i e, ae onau ical, and packaging indus ies. The second pa o his s udy desc ibes ce amic ma e ials wi h a ocus on silica e ce amics. Talc and kaolini e ep esen he main na u al aw ma e ials o adi ional ce amic applica ions. Less adi ional co die i e, s ea i e, and o s e i e could o e p ope y enhancemen and seem o be use ul in elec onics, elec ical enginee ing, ca alys s, sola he mal s o age, o medical applica ions. Keywo ds: clay; mon mo illoni e; nano ille ; ce amics; nanocomposi e 1. In oduc ion In he las cen u y, he esea ch in he a ea o nano echnology s a ed new echnological de elopmen . The e m “nano echnology” was used i s by he Japanese scien is No io Taniguchi in 1974 [ 1 ]. Nano echnology wo ks in he a ea o inc edibly small dimensions, in he ange o 1–100 nm. A nanome e (nm) is 10 −9 m, smalle han he wa eleng h o isible ligh and a hund ed- housand h he wid h o a human hai . In some senses, nanoscience and nano echnologies a e no new. Nanos uc u ed and nanocomposi e ma e ials a e commonly ound in na u e and li ing beings (such as bone) [ 2 ]. Also, chemis s make polyme s, which a e la ge molecules made up o nanoscale subuni s [3]. “Syn he ic” polyme /clay nanocomposi es ha e hei o igin in he pionee ing e- sea ch a Toyo a Cen al Resea ch Labo a o ies. In addi ion, he i s p ac ical applica ion o nanocomposi es, he nylon/mon mo illoni e iming bel co e on he Toyo a Cam y au omobile, ela es o his company as well. Nowadays, he PA/clay nanocomposi es ha e he la ges comme cial p esence in he applica ion ield. The global nanocomposi es ma ke size was USD 5.6 billion in 2022 and is likely o each USD 18.3 billion by 2031 [ 4 ]. The ma ke g ow h is a ibu ed o he apid inc ease in he use o nanocomposi es in biomedical applica ions and packaging. Fu he , ising demand o nanocomposi es has been eco ded also in he sec o s o a ia ion, spo ing goods, and au omobile pa s [4]. Despi e he de elopmen in he a ea o polyme nanocomposi es and hei expanding use in di e en applica ions, esea ch in polyme science and nano echnology con inues. Mine als 2024,14, 93. h ps://doi.o g/10.3390/min14010093 h ps://www.mdpi.com/jou nal/mine als Mine als 2024,14, 93 2 o 24 Especially, i is necessa y o unde s and he p inciples o nanocomposi e beha io a he nanome ic le el. Clays and clay mine als ha e been accompanying humans since he dawn o his o y. Clays and clay mine als, aw o a e modi ica ion, ha e g ea impo ance in a wide a ie y o applica ions mainly due o hei abundan , inexpensi e, ine ness, s abili y, eac i i y, and en i onmen ally iendly [ 5 , 6 ]. Clays a e na u ally occu ing ma e ials consis ing p ima ily o he a ious clay mine als con en and deg ee o pu i y [ 5 , 7 – 9 ]. Clay mine als belong o he phyllosilica e g oup wi h a laye ed s uc u e and wi h one dimension in he nanome e ange [ 5 , 9 ]. The p incipal building elemen s o he clay mine als a e wo-dimensional shee s o silicon-oxygen e ahed al and wo-dimensional shee s o aluminum- o magnesium- oxygen-hyd oxyl oc ahed al [ 10 ]. Indi idual clay mine als, such as kaolin, clay, ben oni e, and e miculi e, di e signi ican ly in hei composi ion and c ys al s uc u e which causes di e en physical and chemical p ope ies (e.g., pa icle size, su ace chemis y, su ace a ea, iscosi y, plas ici y, abso p ion, and adso p ion) [ 7 , 8 , 11 ]. In many cases, he clays o clay mine als can be modi ied o ob ain imp o ed mechanical, he mal, s uc u al, o unc ional p ope ies. Clays and clay mine als ha e many indus ial applica ions such as ce amics [ 12 , 13 ], pape coa ings [ 14 , 15 ], pes icides [ 16 ], pain s [ 17 , 18 ], pha maceu icals [ 19 , 20 ], ag icul- u e [ 21 , 22 ], cons uc ion indus y [ 23 ], ion exchange s, sepa a o s, plas ics [ 24 – 26 ], cos- me ics [ 27 ], insula ions [ 28 ], and elec ical applica ions. Clay mine als can also be used as a good adso ben o wa e pu i ica ion due o lamella s uc u e, high ca ion exchange capaci y, po e size dis ibu ion, and la ge su ace a ea [ 29 ]. Mo eo e , conside able a en- ion ob ained he clay composi e o nanocomposi e ma e ials which can be inco po a ed in o many a eas such as biomedical, cons uc ion, au omobile, emedia ion echnology, pe oleum indus y, was ewa e , ea men , ae ospace, and nano echnology [30]. In ce amic echnology, he mos impo an and mos widely used na u al aw ma e ials also belong o clay mine als such as kaolini e, illi e, mon mo illoni e, alc, py ophylli e, and se pen ine [ 31 ]. Gene ally, ce amic ma e ials show a combina ion o use ul p ope ies such as high s eng h and s i ness a e y high empe a u es, chemical ine ness, and low densi y. Thei applica ions a e es ic ed owing o hei b i le beha io . Co die i e, ens a i e, and o s e i e a e silica e ma e ials ha o m he main componen s o he e na y sys em MgO-Al 2 O 3 -SiO 2 . One o he me hods o he syn hesis o hese ce amic ypes is he sin e ing o na u al aw ma e ials including clay and clay mine als, especially kaolini e, alc, and a combina ion o bo h mine als. The impo an p ope ies ela ing o applica- ions o clay mine als in he ce amic indus y a e plas ici y, chemical and mine alogical composi ion, he mal p ope ies, colo , and mechanical s eng h a e i ing [ 32 ]. Ex ensi e esea ch is also ca ied ou in he ield o ce amics. Nanoce amics ha e eme ged as aluable ma e ials in biomedicine and medical echnology (o hopedics and bone issue enginee - ing). In bone epai , nanoce amics se e as nano sca olds o suppo and acili a e bone g ow h. Applica ions in ene gy s o age, coa ing sys ems, en i onmen al echnology (wa e ea men ), chemis y, cons uc ion, elec onics, and ba e ies ha e also been epo ed [ 33 ]. This e iew is di ided in o wo main pa s. The i s pa desc ibes he use o clays and clay mine als in nanocomposi es mainly in polyme /clay nanocomposi es and hei applica ions. The second pa , conce ning ce amic ma e ials, p o ides a summa y o clay and clay mine als used in p e-ce amic mix u es, ypes o inal silica e ce amics, and hei applica ions. 2. Polyme /Clay Nanocomposi es 2.1. Nano ille Sou ces Nanopa icles ha e a leas one cha ac e is ic leng h scale ha is o he o de o nanome- e s and can ange om iso opic o highly aniso opic needle-like o shee -like elemen s. These nanoelemen s can lead o ul a-la ge in e acial a eas be ween he cons i uen s. In addi ion, he dis ance be ween he nanoelemen s begins o app oach molecula dimensions a ex emely low loading o he nanopa icles. This la ge in e nal in e acial a ea and he Mine als 2024,14, 93 3 o 24 nanoscopic dimensions be ween cons i uen s di e en ia e polyme nanocomposi es om adi ional composi es [ 34 ]. Nano ille s can be di e en ypes o ma e ials like ca bon nano ubes, ulle enes, ca bon black, polyhed al oligome ic silsesquioxanes (POSS), silica, and phyllosilica es (mon o illoni e, halloysi e, and e miculi e). MXene, nano ibe s, me als, and hei oxides a e also used. One o he mos common sou ces o nano ille s is a clay mine al called mon mo illoni e (MMT). Mon mo illoni e Mon mo illoni e has become one o he mos widely used mine als as nano ille s, because o he e sa ili y o eac ions, laye ed mo phology wi h a high aspec a io, and la ge speci ic a ea, which o e s subs an ial ca ion exchange capaci ies. Addi ionally, MMT is comme cially a ailable. MMT is a na u ally occu ing mine al de i ed om he wea he ing o olcanic ash. This mine al belongs o he clay mine als o he smec i e amily. MMT ep esen s 2:1 laye ed aluminous-silica e. The sugges ed c ys allog aphic s uc u e o mon mo illoni e is in Figu e 1[ 35 ]. Isomo phous subs i u ions o Si 4+ o Al 3+ in he e ahed al la ice and o Al 3+ o Mg 2+ in he oc ahed al shee cause an excess o nega i e cha ges wi hin he mon mo illoni e laye s. All a oms may also be eplaced by Fe 3+ , Ti, Ni, Zn, C , and Mn [ 36 ]. In many mine als, an a om o lowe posi i e alence eplaces one o highe alence. These nega i e cha ges a e coun e balanced by ca ions such as Ca 2+ and Na + si ua ed be ween he laye s. Mine als 2024, 14, x FOR PEER REVIEW 3 o 25 Nanopa icles ha e a leas one cha ac e is ic leng h scale ha is o he o de o na- nome e s and can ange om iso opic o highly aniso opic needle-like o shee -like ele- men s. These nanoelemen s can lead o ul a-la ge in e acial a eas be ween he cons i u- en s. In addi ion, he dis ance be ween he nanoelemen s begins o app oach molecula dimensions a ex emely low loading o he nanopa icles. This la ge in e nal in e acial a ea and he nanoscopic dimensions be ween cons i uen s di e en ia e polyme nano- composi es om adi ional composi es [34]. Nano ille s can be di e en ypes o ma e i- als like ca bon nano ubes, ulle enes, ca bon black, polyhed al oligome ic silsesquioxanes (POSS), silica, and phyllosilica es (mon o illoni e, halloysi e, and e miculi e). MXene, nano ibe s, me als, and hei oxides a e also used. One o he mos common sou ces o nano ille s is a clay mine al called mon mo illoni e (MMT). 2.1.1. Mon mo illoni e Mon mo illoni e has become one o he mos widely used mine als as nano ille s, because o he e sa ili y o eac ions, laye ed mo phology wi h a high aspec a io, and la ge speci ic a ea, which o e s subs an ial ca ion exchange capaci ies. Addi ionally, MMT is comme cially a ailable. MMT is a na u ally occu ing mine al de i ed om he wea he ing o olcanic ash. This mine al belongs o he clay mine als o he smec i e amily. MMT ep esen s 2:1 lay- e ed aluminous-silica e. The sugges ed c ys allog aphic s uc u e o mon mo illoni e is in Figu e 1 [35]. Isomo phous subs i u ions o Si4+ o Al3+ in he e ahed al la ice and o Al3+ o Mg2+ in he oc ahed al shee cause an excess o nega i e cha ges wi hin he mon - mo illoni e laye s. All a oms may also be eplaced by Fe3+, Ti, Ni, Zn, C , and Mn [36]. In many mine als, an a om o lowe posi i e alence eplaces one o highe alence. These nega i e cha ges a e coun e balanced by ca ions such as Ca2+ and Na+ si ua ed be ween he laye s. Figu e 1. Chemical s uc u e o smec i e clay [35]. Figu e 1. Chemical s uc u e o smec i e clay [35]. Due o he high hyd ophilici y o mon mo illoni e, wa e molecules a e usually also p esen be ween he laye s. S acking o he laye s leads o egula an de Waals gaps called in e laye s o galle ies. The sum o he single laye hickness and he in e laye ep esen s he epea uni o he mul ilaye ma e ial, so-called d-spacing o basal spacing. 2.2. Clay O ganophiliza ion The main di icul ies o polyme /clay nanocomposi es ela e o he hyg oscopic cha ac e o clay and clay mine als. I is ela i ely simple o dispe se clay in wa e o wa e - Mine als 2024,14, 93 4 o 24 soluble polyme monome s, bu clay dispe sed in a high molecula hyd ophobic polyme is like ying o mix oil in wa e . The eason o such beha io is he di e en na u e o hese wo ma e ials as was men ioned abo e. O ganophilic polyme s a e no miscible wi h p is ine hyd ophilic clay ep esen ed in ou case by mon mo illoni e (MMT). This phe- nomenon is a ibu ed o he highe su ace ene gy o MMT compa ed o a mac omolecula ma ix which ends o c ea e a s onge cohesi e in e ac ion be ween clay laye s and u he hampe he inclusion o polyme chains in o he in e lamella egion o MMT [ 37 – 41 ]. The e o e, su ace modi ica ion o MMT plays a e y impo an ole in clay inco po a ion in o he polyme ma ix. The p ocess leading o nanocomposi e is called delamina ion o ex olia ion o mon mo illoni e o indi idual shee s. On he o he hand, he hyd ophilic ea u e o he MMT su ace pe mi s wa e and o he pola molecules o in e cala e in o he galle ies wi hin clay laye s [37]. The clay modi ica ion p ocess, called in e cala ion (1 chemical agen ) o co-in e cala ion (2 o mo e chemical agen s), can be de ined as he e e sible inclusion o a molecule o ion in o ille wi h a laye ed s uc u e. In he case o laye ed aluminous silica es (phylosilica es), in e cala ion means in e calan pene a ion in o he clay-laye ed s uc u e. The esul o such a success ul p ocess is an inc ease in d-spacing, Figu e 2. Nex , he changes depend on he ype o used in e calan , i s concen a ion, and he leng h o he chain. The clay a ini y o he polyme su ace is in luenced and he in e cala ion mo e compa ible mon mo illoni e- polyme in e ace can be hen de eloped. Mine als 2024, 14, x FOR PEER REVIEW 4 o 25 Due o he high hyd ophilici y o mon mo illoni e, wa e molecules a e usually also p esen be ween he laye s. S acking o he laye s leads o egula an de Waals gaps called in e laye s o galle ies. The sum o he single laye hickness and he in e laye ep- esen s he epea uni o he mul ilaye ma e ial, so-called d-spacing o basal spacing. 2.2. Clay O ganophiliza ion The main di icul ies o polyme /clay nanocomposi es ela e o he hyg oscopic cha - ac e o clay and clay mine als. I is ela i ely simple o dispe se clay in wa e o wa e - soluble polyme monome s, bu clay dispe sed in a high molecula hyd ophobic polyme is like ying o mix oil in wa e . The eason o such beha io is he di e en na u e o hese wo ma e ials as was men ioned abo e. O ganophilic polyme s a e no miscible wi h p is ine hyd ophilic clay ep esen ed in ou case by mon mo illoni e (MMT). This phe- nomenon is a ibu ed o he highe su ace ene gy o MMT compa ed o a mac omolecu- la ma ix which ends o c ea e a s onge cohesi e in e ac ion be ween clay laye s and u he hampe he inclusion o polyme chains in o he in e lamella egion o MMT [37– 41]. The e o e, su ace modi ica ion o MMT plays a e y impo an ole in clay inco po- a ion in o he polyme ma ix. The p ocess leading o nanocomposi e is called delamina- ion o ex olia ion o mon mo illoni e o indi idual shee s. On he o he hand, he hyd o- philic ea u e o he MMT su ace pe mi s wa e and o he pola molecules o in e cala e in o he galle ies wi hin clay laye s [37]. The clay modi ica ion p ocess, called in e cala ion (1 chemical agen ) o co-in e cala- ion (2 o mo e chemical agen s), can be de ined as he e e sible inclusion o a molecule o ion in o ille wi h a laye ed s uc u e. In he case o laye ed aluminous silica es (phy- losilica es), in e cala ion means in e calan pene a ion in o he clay-laye ed s uc u e. The esul o such a success ul p ocess is an inc ease in d-spacing, Figu e 2. Nex , he changes depend on he ype o used in e calan , i s concen a ion, and he leng h o he chain. The clay a ini y o he polyme su ace is in luenced and he in e cala ion mo e compa ible mon mo illoni e-polyme in e ace can be hen de eloped. Figu e 2. P ocess o mon mo illoni e in e cala ion. Amino acids we e employed as he i s in e calan s in he syn hesis o nanocompo- si es (polyamide 6-clay hyb ids) [42]. Nume ous o he kinds o in e calan agen s ha e been used in he syn hesis o nanocomposi es oday’s. The mos popula a e ca ionic su - ac an s, such as alkylammonium ions, because hey can be exchanged easily wi h he ions si ua ed be ween he clay laye s. All he comme cial ypes o mon mo illoni es a e based on hese subs ances. This kind o su ac an consis s o wo dis inc pa s, a posi i ely cha ged hyd ophilic head and a hyd ophobic hyd oca bon chain ail. A e modi ica ion, ca ionic su ac an molecules a ach o he inne and ou e su ace o clay mine als and hus al e he su ace p ope ies o clay mine als om hyd ophilic o hyd ophobic [43]. In addi ion, silanes ha e been used because o hei abili y o eac wi h he hyd oxyl g oups si ua ed a he su ace and he edges o he clay laye s. Smec i e o ganically in e cala ed s uc u es we e i s s udied by Lagaly and Weis in 1969. A e modi ica ion, se e al a angemen s inside he in e laye a e possible Figu e 3. Lagaly and Weis ound wo possible a angemen s o o ganic molecules in he in e laye , namely la e al and pe pendicula (pa a in) [44,45]. A p esen h ee basic me hods o in e cala ion a e pe o med: Figu e 2. P ocess o mon mo illoni e in e cala ion. Amino acids we e employed as he i s in e calan s in he syn hesis o nanocomposi es (polyamide 6-clay hyb ids) [ 42 ]. Nume ous o he kinds o in e calan agen s ha e been used in he syn hesis o nanocomposi es oday’s. The mos popula a e ca ionic su ac an s, such as alkylammonium ions, because hey can be exchanged easily wi h he ions si ua ed be ween he clay laye s. All he comme cial ypes o mon mo illoni es a e based on hese subs ances. This kind o su ac an consis s o wo dis inc pa s, a posi i ely cha ged hyd ophilic head and a hyd ophobic hyd oca bon chain ail. A e modi ica ion, ca ionic su ac an molecules a ach o he inne and ou e su ace o clay mine als and hus al e he su ace p ope ies o clay mine als om hyd ophilic o hyd ophobic [ 43 ]. In addi ion, silanes ha e been used because o hei abili y o eac wi h he hyd oxyl g oups si ua ed a he su ace and he edges o he clay laye s. Smec i e o ganically in e cala ed s uc u es we e i s s udied by Lagaly and Weis in 1969. A e modi ica ion, se e al a angemen s inside he in e laye a e possible Figu e 3. Lagaly and Weis ound wo possible a angemen s o o ganic molecules in he in e laye , namely la e al and pe pendicula (pa a in) [44,45]. A p esen h ee basic me hods o in e cala ion a e pe o med: 1. Ion-exchange me hod is based on he MMT’s abili y o so b some ypes o ca ions and o keep hem in he change s a e [46,47]. 2. Ion-dipole me hod is based on he ion-dipole in e ac ion o an o ganic in e calan and an in e laye ca ion [48] 3. G a ing, he o ma ion o a co alen linkage be ween he clay pla ele and he hy- d ophobic pa o he coupling agen [37]. Mine als 2024,14, 93 5 o 24 Mine als 2024, 14, x FOR PEER REVIEW 5 o 25 1. Ion-exchange me hod is based on he MMT’s abili y o so b some ypes o ca ions and o keep hem in he change s a e [46,47]. 2. Ion-dipole me hod is based on he ion-dipole in e ac ion o an o ganic in e calan and an in e laye ca ion [48] 3. G a ing, he o ma ion o a co alen linkage be ween he clay pla ele and he hyd o- phobic pa o he coupling agen [37]. Figu e 3. Alkyl chain a angemen in laye ed silica es: (a) la e al monolaye , (b) la e al bilaye , (c) pa a in (monolaye ), and (d) pa a in ype bilaye . 2.2.1. Ion-Exchange In e cala ion A cha ac e is ic ea u e o smec i es such as mon mo illoni e is hei abili y o so b ce ain ca ions and e ain hem in an exchangeable s a e. I means ha hese in e cala ed ca ions can be exchanged by ea men o o he ca ions in a wa e solu ion (we me hod), Figu e 4. The mos common exchangeable ca ions a e Na+, Ca2+, Mg2+, H+, K+, and NH4+. Indeed, i he clay is placed in a solu ion o a gi en elec oly e, an exchange occu s be ween he ions o he clay (X+) and hose o he elec oly e (Y+): Figu e 4. De elopmen o o ganoclay ea ed wi h qua e na y sal : ion-exchange in e cala ion me hod [49]. Figu e 3. Alkyl chain a angemen in laye ed silica es: (a) la e al monolaye , (b) la e al bilaye , (c) pa a in (monolaye ), and (d) pa a in ype bilaye . 2.2.1. Ion-Exchange In e cala ion A cha ac e is ic ea u e o smec i es such as mon mo illoni e is hei abili y o so b ce ain ca ions and e ain hem in an exchangeable s a e. I means ha hese in e cala ed ca ions can be exchanged by ea men o o he ca ions in a wa e solu ion (we me hod), Figu e 4. The mos common exchangeable ca ions a e Na + , Ca 2+ , Mg 2+ , H + , K + , and NH 4+ . Indeed, i he clay is placed in a solu ion o a gi en elec oly e, an exchange occu s be ween he ions o he clay (X+) and hose o he elec oly e (Y+): X+−Mon mo illoni e +Y−⇄Y+−Mon mo illoni e−+X+ Mine als 2024, 14, x FOR PEER REVIEW 5 o 25 1. Ion-exchange me hod is based on he MMT’s abili y o so b some ypes o ca ions and o keep hem in he change s a e [46,47]. 2. Ion-dipole me hod is based on he ion-dipole in e ac ion o an o ganic in e calan and an in e laye ca ion [48] 3. G a ing, he o ma ion o a co alen linkage be ween he clay pla ele and he hyd o- phobic pa o he coupling agen [37]. Figu e 3. Alkyl chain a angemen in laye ed silica es: (a) la e al monolaye , (b) la e al bilaye , (c) pa a in (monolaye ), and (d) pa a in ype bilaye . 2.2.1. Ion-Exchange In e cala ion A cha ac e is ic ea u e o smec i es such as mon mo illoni e is hei abili y o so b ce ain ca ions and e ain hem in an exchangeable s a e. I means ha hese in e cala ed ca ions can be exchanged by ea men o o he ca ions in a wa e solu ion (we me hod), Figu e 4. The mos common exchangeable ca ions a e Na+, Ca2+, Mg2+, H+, K+, and NH4+. Indeed, i he clay is placed in a solu ion o a gi en elec oly e, an exchange occu s be ween he ions o he clay (X+) and hose o he elec oly e (Y+): Figu e 4. De elopmen o o ganoclay ea ed wi h qua e na y sal : ion-exchange in e cala ion me hod [49]. Figu e 4. De elopmen o o ganoclay ea ed wi h qua e na y sal : ion-exchange in e cala ion me hod [ 49 ]. Fo gi en clay, he maximum numbe o ca ions ha can be aken up is cons an and known as he ca ion-exchange capaci y (CEC). CEC is measu ed in milliequi alen s pe g am (meq/g) o mo e equen ly pe 100 g (meq/100 g). Ca ion-exchange capaci y measu emen s a e pe o med a a neu al pH o 7. The CEC o mon mo illoni e a ies om 80 o 150 meq/100 g [ 50 ]. In he dependence on he CEC and he cha ac e o o ganoca ion, di e en s uc u es can be c ea ed in he in e laye space. These s uc u es could be help ul Mine als 2024,14, 93 6 o 24 du ing he nanocomposi e compounding and o he igh choice o in e calan . The success ul MMT in e cala ion and ollowing ex olia ion p ocess du ing compounding is a good assump ion o enhancemen o inal ma e ials p ope ies. 2.2.2. Ion-Dipole In e cala ion Ion-dipole me hod is based on ion-dipole in e ac ion. This me hod di e s om he ion- exchange app oach in ha he exchangeable ca ion (pa ial posi i e cha ge) emains on he clay su ace, Figu e 5. I means ha i is no necessa y o abla e any p oduc o a chemical eac ion. Nex ion-dipole app oach ad an age ela es o he non-wa e en i onmen (d y me hod). As he in e calan s, alkylamine (oc adecylamine (ODA), dodecylamine (DDA)), and p ima y amine can be used. As he compa ibilize he common plas ics p ocessing aid, like plas icize s, lub ican s, and o he modi ie s, could also be sui able [ 51 – 53 ]. The in e cala e s uc u e depends on he concen a ion o used o ganic in e calan , in he gues - gues and gues -hos in e ac ions. This echnique is also possible o apply o p ocess co-in e cala ion [54,55]. Mine als 2024, 14, x FOR PEER REVIEW 6 o 25 Fo gi en clay, he maximum numbe o ca ions ha can be aken up is cons an and known as he ca ion-exchange capaci y (CEC). CEC is measu ed in milliequi alen s pe g am (meq/g) o mo e equen ly pe 100 g (meq/100 g). Ca ion-exchange capaci y meas- u emen s a e pe o med a a neu al pH o 7. The CEC o mon mo illoni e a ies om 80 o 150 meq/100 g [50]. In he dependence on he CEC and he cha ac e o o ganoca ion, di e en s uc u es can be c ea ed in he in e laye space. These s uc u es could be help- ul du ing he nanocomposi e compounding and o he igh choice o in e calan . The success ul MMT in e cala ion and ollowing ex olia ion p ocess du ing compounding is a good assump ion o enhancemen o inal ma e ials p ope ies. 2.2.2. Ion-Dipole In e cala ion Ion-dipole me hod is based on ion-dipole in e ac ion. This me hod di e s om he ion-exchange app oach in ha he exchangeable ca ion (pa ial posi i e cha ge) emains on he clay su ace, Figu e 5. I means ha i is no necessa y o abla e any p oduc o a chemical eac ion. Nex ion-dipole app oach ad an age ela es o he non-wa e en i on- men (d y me hod). As he in e calan s, alkylamine (oc adecylamine (ODA), dodecyla- mine (DDA)), and p ima y amine can be used. As he compa ibilize he common plas ics p ocessing aid, like plas icize s, lub ican s, and o he modi ie s, could also be sui able [51– 53]. The in e cala e s uc u e depends on he concen a ion o used o ganic in e calan , in he gues -gues and gues -hos in e ac ions. This echnique is also possible o apply o p ocess co-in e cala ion [54,55]. Figu e 5. Ion-dipole in e cala ion me hod. 2.2.3. G a ing The g a ing app oach has a ac ed scien is s o e he las 15 yea s. The me hod is based on he o ma ion o co alen bonds be ween he mon mo illoni e pla ele su ace and he hyd ophobic modi ie . This me hod can imp o e he s abili y o o ganophilized clay su aces. The mos amous modi ie s a e silanes, he e o e his p ocess is called si- laniza ion o silyla ion. Alkoxysilane and chlo osilane a e he mos common in e cala es. Howe e , chlo osilane is no used oo o en due o i s endency o c ea e HCl du ing he g a ing p ocess [56]. In addi ion o inc eased he mal s abili y, clay ea men by his ap- p oach o e s i e e sible coupling and igh ly secu es he agen on he clay su ace, a oid- ing elease in o he en i onmen o cause ad e se e ec s [57]. O ganosilanes also se e as a key b idge o enhance he in e acial in e ac ion be ween he silyla ed-MMT and he polyme ma ix owing o he educed clay su ace ene gy because o silane g a ing, hus enabling be e dispe sibili y o he ein o cing phase in he con inuous ma ix [37,58]. 2.3. Clay Applica ion in Nanocomposi es Gene ally, nanocomposi es ep esen ma e ials wi h mul iphase ul a ine s uc u es wi h a leas one dimension 10−9 m. In he case o polyme /clay nanocomposi es, hey a e o med h ough he connec ion o wo di e en ma e ials, o ganic (polyme ) and ino - ganic (mine al). The nex impo an ea u es o polyme nanocomposi es a e low con en o ille (1%–5%) compa ed o con en ional composi es (30%–50%), anspa ency, and Figu e 5. Ion-dipole in e cala ion me hod. 2.2.3. G a ing The g a ing app oach has a ac ed scien is s o e he las 15 yea s. The me hod is based on he o ma ion o co alen bonds be ween he mon mo illoni e pla ele su ace and he hyd ophobic modi ie . This me hod can imp o e he s abili y o o ganophilized clay su aces. The mos amous modi ie s a e silanes, he e o e his p ocess is called silaniza ion o silyla ion. Alkoxysilane and chlo osilane a e he mos common in e cala es. Howe e , chlo osilane is no used oo o en due o i s endency o c ea e HCl du ing he g a ing p ocess [ 56 ]. In addi ion o inc eased he mal s abili y, clay ea men by his app oach o e s i e e sible coupling and igh ly secu es he agen on he clay su ace, a oiding elease in o he en i onmen o cause ad e se e ec s [ 57 ]. O ganosilanes also se e as a key b idge o enhance he in e acial in e ac ion be ween he silyla ed-MMT and he polyme ma ix owing o he educed clay su ace ene gy because o silane g a ing, hus enabling be e dispe sibili y o he ein o cing phase in he con inuous ma ix [37,58]. 2.3. Clay Applica ion in Nanocomposi es Gene ally, nanocomposi es ep esen ma e ials wi h mul iphase ul a ine s uc u es wi h a leas one dimension 10 −9 m. In he case o polyme /clay nanocomposi es, hey a e o med h ough he connec ion o wo di e en ma e ials, o ganic (polyme ) and ino ganic (mine al). The nex impo an ea u es o polyme nanocomposi es a e low con en o ille (1%–5%) compa ed o con en ional composi es (30%–50%), anspa ency, and la ge changes in ma e ial p ope ies, like E-modulus, s eng h, sh inkage, densi y, chemical and i e esis ance, e c. The polyme nanocomposi es could be di ided in o se e al g oups acco ding o he dimensions o he dispe sed nanoscale: 1. Two-dimensional (2D) nanoma e ials—2 dimensions in mac oscale (laye ed sili- ca e [ 59 – 61 ], g aphene [ 62 , 63 ] o MXene [ 64 , 65 ]—lamella nano ille s in he o m o shee s o one o a ew nanome es hick and hund eds o housands o nanome es long and wide). Mine als 2024,14, 93 7 o 24 2. One-dimensional (1D) nanoma e ials—2dimensions in nanome es and he hi d is la ge (nano ibe s o nano ubes, e.g., ca bon nano ib es and nano ubes [ 66 ] o halloysi e nano ubes [67–69]— ib illa nanoscale). 3. Ze o-dimensional (0D) s uc u es—0 dimensions in mac oscale (sphe ical silica [ 70 , 71 ], semiconduc o nanoclus e s [ 72 ] and quan um do s [ 73 ], and isodimensional sphe ical pa icles) [74,75]. One o he p ocessing p oblems o nanocomposi es is he nano ille ex olia ion du - ing p ocessing. The e o e, polyme /clay sys ems a e di ided in o ou gene al g oups acco ding o he nano ille ex olia ion le el (Figu e 6): 1. Mic ocomposi e, whe e he clay ac s as a con en ional ille . The inal ma e ial belongs o adi ional composi e ma e ials. 2. In e cala ed nanocomposi e consis s o a egula inse ion o he polyme be ween he clay laye s. The inal ma e ial belongs o nanocomposi es. 3. In e cala ed and pa ially delamina ed nanocomposi es, an in e media e s ep be ween in e cala ed and ex olia ed s uc u e. The inal ma e ial belongs o nanocomposi es. 4. Ex olia ed nanocomposi e whe e he ille is delamina ed o 1 nm- hick laye s. The inal ma e ial belongs o nanocomposi es. Mine als 2024, 14, x FOR PEER REVIEW 7 o 25 la ge changes in ma e ial p ope ies, like E-modulus, s eng h, sh inkage, densi y, chem- ical and i e esis ance, e c. The polyme nanocomposi es could be di ided in o se e al g oups acco ding o he dimensions o he dispe sed nanoscale: 1. Two-dimensional (2D) nanoma e ials—2 dimensions in mac oscale (laye ed silica e [59–61], g aphene [62,63] o MXene [64,65]—lamella nano ille s in he o m o shee s o one o a ew nanome es hick and hund eds o housands o nanome es long and wide). 2. One-dimensional (1D) nanoma e ials—2dimensions in nanome es and he hi d is la ge (nano ibe s o nano ubes, e.g., ca bon nano ib es and nano ubes [66] o hal- loysi e nano ubes [67–69]— ib illa nanoscale). 3. Ze o-dimensional (0D) s uc u es—0 dimensions in mac oscale (sphe ical silica [70,71], semiconduc o nanoclus e s [72] and quan um do s [73], and isodimensional sphe ical pa icles) [74,75]. One o he p ocessing p oblems o nanocomposi es is he nano ille ex olia ion du - ing p ocessing. The e o e, polyme /clay sys ems a e di ided in o ou gene al g oups ac- co ding o he nano ille ex olia ion le el (Figu e 6): 1. Mic ocomposi e, whe e he clay ac s as a con en ional ille . The inal ma e ial be- longs o adi ional composi e ma e ials. 2. In e cala ed nanocomposi e consis s o a egula inse ion o he polyme be ween he clay laye s. The inal ma e ial belongs o nanocomposi es. 3. In e cala ed and pa ially delamina ed nanocomposi es, an in e media e s ep be ween in e cala ed and ex olia ed s uc u e. The inal ma e ial belongs o nanocomposi es. 4. Ex olia ed nanocomposi e whe e he ille is delamina ed o 1 nm- hick laye s. The inal ma e ial belongs o nanocomposi es. Figu e 6. Polyme /clay nanocomposi e classi ica ion. 2.3.1. Polyme /Clay Nanocomposi e P ocessing The inal s ep o nanocomposi e p epa a ion is he o ganoclay mixing wi h polyme . Ea ly expe imen s wi h clay- illed polyme s equi ed p ocessing ha was no comme - cially iendly, bu his si ua ion has changed. A p ima y di icul y is he p ope dispe - sion o he ille in he polyme ma ix. Wi hou good dispe sion and ille dis ibu ion, Figu e 6. Polyme /clay nanocomposi e classi ica ion. 2.3.1. Polyme /Clay Nanocomposi e P ocessing The inal s ep o nanocomposi e p epa a ion is he o ganoclay mixing wi h polyme . Ea ly expe imen s wi h clay- illed polyme s equi ed p ocessing ha was no comme cially iendly, bu his si ua ion has changed. A p ima y di icul y is he p ope dispe sion o he ille in he polyme ma ix. Wi hou good dispe sion and ille dis ibu ion, he high su ace a ea is comp omised, and he agg ega es can ac as de ec s, which limi s hei p ope ies [ 2 ]. Se e al s a egies ha e been conside ed o p epa e polyme /mon mo illoni e nanocomposi es (Figu e 7) [76]: 1. In-si u polyme iza ion me hod, in e cala ion o a sui able monome ollowed by polyme iza ion. The i s me hod used o syn hesize polyme /clay nanocomposi es is based on polyamide 6. 2. Solu ion me hod, in e cala ion o dissol ed polyme om a solu ion. The d awback o his me hod is he equi emen o a sui able sol en . I has been shown ha in e cala ion only occu s o ce ain polyme /sol en o monome /sol en pai s [ 77 ]. Mine als 2024,14, 93 8 o 24 Nanocomposi es based on high-densi y polye hylene [ 78 ], and polyimide [ 79 ] can be syn hesized by his me hod. 3. Mel in e cala ion me hod, mixing he clay (usually o ganoclay) wi h he polyme ma ix abo e i s so ening poin in ei he s a ic o low condi ions. The polyme chains sp ead om he mol en mass in o he silica e galle ies o o m ei he in e cala ed o delamina ed hyb ids acco ding o he deg ee o pene a ion [ 56 ]. This p ocess was i s epo ed by Vaia e al. [ 80 ] in 1993. This me hod is ela i ely easy and allows o he use o cu en p ocessing equipmen o nanocomposi e echnology. T adi ional p ocessing echniques could be used o mel in e cala ion, like a wo- oll mill, win-sc ew ex ude (PA, PP, PE, and PVC), injec ion molding, blow molding, and he mal sp aying [2]. Mine als 2024, 14, x FOR PEER REVIEW 8 o 25 he high su ace a ea is comp omised, and he agg ega es can ac as de ec s, which limi s hei p ope ies [2]. Se e al s a egies ha e been conside ed o p epa e polyme /mon mo- illoni e nanocomposi es (Figu e 7) [76]: 1. In-si u polyme iza ion me hod, in e cala ion o a sui able monome ollowed by polyme iza ion. The i s me hod used o syn hesize polyme /clay nanocomposi es is based on polyamide 6. 2. Solu ion me hod, in e cala ion o dissol ed polyme om a solu ion. The d awback o his me hod is he equi emen o a sui able sol en . I has been shown ha in e - cala ion only occu s o ce ain polyme /sol en o monome /sol en pai s [77]. Nanocomposi es based on high-densi y polye hylene [78], and polyimide [79] can be syn hesized by his me hod. 3. Mel in e cala ion me hod, mixing he clay (usually o ganoclay) wi h he polyme ma ix abo e i s so ening poin in ei he s a ic o low condi ions. The polyme chains sp ead om he mol en mass in o he silica e galle ies o o m ei he in e ca- la ed o delamina ed hyb ids acco ding o he deg ee o pene a ion [56]. This p o- cess was i s epo ed by Vaia e al. [80] in 1993. This me hod is ela i ely easy and allows o he use o cu en p ocessing equipmen o nanocomposi e echnology. T adi ional p ocessing echniques could be used o mel in e cala ion, like a wo- oll mill, win-sc ew ex ude (PA, PP, PE, and PVC), injec ion molding, blow mold- ing, and he mal sp aying [2]. Figu e 7. Illus a ion o (a) in si u polyme iza ion, (b) mel in e cala ion, and (c) solu ion in e cala- ion [76]. Highly pola polyme s such as Nylon [81–83] o polyimides [84,85] a e mo e easily in e cala ed han non-pola polyme s such as polyp opylene because pola polyme s ha e a highe a ini y o he pola clay galle ies. In si u polyme iza ion monome in e cala es di ec ly in o he o ganically modi ied clay galle ies and he monome ei he can adso b on o he laye su ace o can be ancho ed by ee adical echniques. Mel in e cala ion in ol es mixing he clay and a polyme mel wi h o wi hou he shea . The success o mel in e ca- la ion is su p ising, gi en ha he galle y spacing is only abou 2 nm and he adius o gy- a ion o he polyme is signi ican ly la ge han his. E en mo e su p ising is ha he speed o mel in e cala ion is as e han ha o he sel -di usion o polyme s and scales wi h he Figu e 7. Illus a ion o (a) in si u polyme iza ion, (b) mel in e cala ion, and (c) solu ion in e cala ion [ 76 ]. Highly pola polyme s such as Nylon [ 81 – 83 ] o polyimides [ 84 , 85 ] a e mo e easily in e cala ed han non-pola polyme s such as polyp opylene because pola polyme s ha e a highe a ini y o he pola clay galle ies. In si u polyme iza ion monome in e cala es di ec ly in o he o ganically modi ied clay galle ies and he monome ei he can adso b on o he laye su ace o can be ancho ed by ee adical echniques. Mel in e cala ion in ol es mixing he clay and a polyme mel wi h o wi hou he shea . The success o mel in e cala ion is su p ising, gi en ha he galle y spacing is only abou 2 nm and he adius o gy a ion o he polyme is signi ican ly la ge han his. E en mo e su p ising is ha he speed o mel in e cala ion is as e han ha o he sel -di usion o polyme s and scales wi h he in e se o he molecula weigh . The esul s o molecula dynamics and expe imen al s udies indica e ha he s onge he clay/polyme in e ac ion, he lowe he in e cala ion a e. In addi ion, laye lexibili y seems o con ol he mechanism o in e cala ion [2]. 2.3.2. Polyme Ma ix Many di e en polyme s ha e al eady been used o p oduce polyme /clay nanocom- posi es. Bo h he moplas ics and he mose s can be success ully u ilized o he p epa a ion o nanocomposi es. In ensi e esea ch is ca ied ou in ubbe mix u es oo. The i s and he mos s udied he moplas ics o he syn hesis o polyme -clay nanocomposi es has been polyamide 6 [ 86 – 91 ]. Polyamide 6/clay hyb ids we e disco e ed by Toyo a e- Mine als 2024,14, 93 9 o 24 sea che s in he ea ly nine ies [ 92 – 95 ] and nowadays hey a e used in au omo i e pa s. The eams dealing wi h hese ma e ials we e concen a ed a ound Usuki A., Kojima Y., Okada A. [92–96] , Azuma H. [ 97 ], Fukusima Y. [ 98 ], Wu T. [ 99 ], De aux, E. [ 100 ], Tanaka G. [101], and U acki L. A. [87,89,90]. Poly inylchlo ide [ 8 , 102 , 103 ] nanocomposi e p ocessing was s udied, in addi ion. Poly inylchlo ide (PVC) is an impo an comme cial polyme . I is one o he mos e sa ile and oldes he moplas ics. I is a ma e ial ha o e s se e al posi i e aspec s like low cos , eco e abili y, acile p ocessing, and excellen elec ical and chemical esis ance. Commonly, PVC is a ailable in wo b oad ca ego ies: lexible PVC (plas icized one), and igid PVC (unplas icized one). The PVC p oduc s ange om piping and siding, doo and window p o iles, blood bags, and ubing, o wi e and cable insula ion and mo e. The i s esul s dealing wi h PVC/MMT nanocomposi es we e p esen ed a he in e na ional con e ences ANTEC ′ 01 and ANTEC ′ 02 in he USA [ 104 , 105 ] by Kalendo a e al. In his s udy, pa ic- ula ly he suspension ype o PVC was employed o he polyme /clay nanocomposi es de elopmen . The o mula ion o he PVC mix u es consis s o 74% o PVC, 24% o plas i- cize , and 2% o s abilize . The na u al ype o mon mo illoni e and he o ganophilized one we e es ed. The mel in e cala ion was employed o p oduce nanocomposi es. One o he impo an ques ions was how long alkyl chains should be used o he ex olia ion o silica e laye s. The e o e, alkylamines wi h di e en alkyl chain leng hs we e es ed as he o ganic compa ibilize . Especially sho e alkyl chains we e es ed as sui able chemical modi ie s o MMT. Fi s ly, Na+ mon mo illoni e was ion-dipole in e cala ed wi h dodecylamine (DDA, 12 C) and oc ylamine (OA, 8C) molecules. The s uc u e o oc adecylamine (ODA, 18 C) ion-dipole in e cala ed in o MMT was desc ibed by Pospisil e al. p e iously [ 106 ]. The ma e ial s uc u e was de e mined based on X- ay di ac ion and molecula simula ion esul s. Molecula mechanics and classical molecula dynamics we e ca ied ou in he Ce ius2 modeling en i onmen . Based on calcula ed alues o in e ac ion ene gies be ween wo gues laye s in he in e laye space o mon mo illoni e and XRD pa e ns, a p obable in e calan molecules a angemen in he MMT in e laye was designed. I was con i med by Pospisil [ 106 ], Figu e 8, ha ODA ion-dipole in e cala ed in o MMT allows he exis ence o sup amolecula s uc u e which is p esen ed by bilaye a angemen alkyl chains pe - pendicula o sligh ly oblique o he aluminosilica e laye . The esul s a e consis en wi h he s udies ca ied ou by Lagaly [ 43 , 107 – 109 ] in he ield o ion-exchange in e cala ion. In addi ion, he Oc ylamine (OA) ion-dipole in e cala ed was also no able o p o ide he bilaye a angemen in he MMT in e laye space. F om he ob ained da a i ollows ha mon mo illoni e in e cala ed wi h sho alkylamine chains sugges s a disad an age o polyme /MMT nanocomposi e p oduc ion. In he pas , he mos impo an equi emen o new syn he ic polyme s was hei e- sis ance o clima e change [ 110 ]. Recen ly esea ch has unde gone subs an ial changes, due o he ecological p oblems caused by non-deg adable polyme li e . These ac s esul ed in he esea ch in he ield o biopolyme s. Cu en ly, biodeg adable polyme s like polylac ic acid (PLA) and Polyhyd oxybu y a e (PHB) a e s udied success ully [ 111 – 115 ]. Poly(lac ic acid) o polylac ide (PLA) has a leading posi ion in he ma ke o biobased polyme s and is one o he mos p omising sus ainable al e na i es o pe oleum-based polyme s [ 116 ]. PLA is no only bio-based bu compos able and biodeg adable h ough hyd olysis by mic oo ganisms [ 117 ]. Recen ly, new echniques o p oduce high molecula weigh PLA wi h ela i ely good p ope ies, ha e led o he expansion o he p oduc po olio om he biomedical a ea o sho se ice li e applica ions (ag icul u e and packaging). None heless, p edisposi ion o deg ada ion, poo he mal esis ance, and unsui able mechanical and ba ie p ope ies limi indus ial applica ion o long- e m pe o mance p oduc s in au omo i e and elec onic indus ies. Fo i ems such as hese, esis ance o deg ada ion is equi ed, unlike o disposable applica ions [ 118 ]. Fu he , high p ice is also an obs acle o g ea e expansion o PLA on he ma ke . To add ess one o hese limi a ions, nanoscale s uc u ed laye ed clay pa icles can be inco po a ed in o PLA con e ing s eng h, inc easing i s gas ba ie p ope ies [ 113 , 119 , 120 ], and ul ima ely Mine als 2024,14, 93 16 o 24 Table 2. Con . P e-ce amic Mix u es Clay Mine als O he Type o Ce amics Sin e ing Tempe a u e ( ◦ C) Applica ions Re . Kaolini e, alc, e miculi e, o gano- e miculi e Co die i e/s ea i e 1300 - [200] Kaolini e, alc, e miculi es Al2O3, Al(OH)3Co die i e 1300 - [187] Kaolini e, alc, e miculi e Al2O3Co die i e 1300 - [191] Kaolini e, alc, e miculi e, o gano- e miculi e Co die i e/s ea i e 1300 - [203] Talc, kaolini e, e miculi e MgO, Al(OH)3Co die i e 1300 - [192] Talc, kaolini e, ball clay Al2O3, silica sand Co die i e 1300 Indus ial manu ac u e o po ous ce amic ma e ials [194] Talc, kaolini e, CeO2/ e miculi e - Co die i e/CeO21300 Pho oca alys s [204,205] Talc Polysiloxane, Al2O3, expandable mic osphe es Co die i e 1300 - [198] Talc, kaolini e Al(OH)3Co die i e 1260 - [189] Kaolin, sepioli e Kaolin, alc Qua z SiO2, eldspa Co die i e Co die i e 1250, 1300, 1350 Applica ion in ound y [201] Talc Fly ash, Al2O3Co die i e 1350 Re ac o y applica ion [197] Talc, kaolin Feldspa , albi e, andalusi e, Al2O3Co die i e/mulli e 1340–1420 The mal s o age ma e ials [207] 4. Conclusions The p esen ed s udy ocuses on one pa o nano echnology a ge ed o polyme science, conc e ely o he ield o polyme /clay nanocomposi es. These hyb id o ganic- ino ganic ma e ials show an in e es ing enhancemen o p ope ies compa ed o adi ional mic o-composi es wi h a low le el o nano ille loading ob iously in he ange o 1%–5%. The mos a o i e sou ce o nanoelemen s is mon mo illoni e (MMT), a laye ed aluminosili- ca e whose mo phology is c ea ed by s acks o indi idual pla ele s wi h 1 nm hickness. Al hough clay nanocomposi es we e disco e ed in he 1990s, in e es om he scien i ic communi y emains high. Some o he applica ions ha e al eady been comme cialized. App oxima ely 80% o he polyme /clay nanocomposi es a e des ined o he au omo i e (Gene al Mo o s, Che ole , Nissan), ae onau ical, and packaging indus ies [ 208 ]. The key d i e s o he use o polyme /clay nanocomposi es in he au omo i e indus y a e educ ion in ehicle’s weigh , imp o ed engine e iciency ( uel sa ing), educ ion in CO 2 emissions, and supe io pe o mance (g ea e sa e y, inc eased com o , and be e d i - abili y) [ 208 ]. The nex pe spec i e is p esen ed by packaging applica ions. The es ed ma e ials based on PLA showed common imp o emen in he ange o 30% [ 113 ]. O he comme cial applica ions include cables, u ni u e, and domes ic appliances. Fu he , appli- ca ions like in selec i e ca alyze s, conduc i e polyme s, il a ion o oxic ma e ials, d ug deli e y sys ems, and ene gy s o age, a e expec ed. Al hough nanocomposi es p esen a se ies o ad anced p ope ies, hei p oduc ion is conside ed low in compa ison wi h o he ma e ials, due o he p oduc ion cos s. The second pa ocused on ce amic ma e ials p epa ed om clay mine als in p e- ce amic mix u es. The kind, quan i y, and combina ion o clay mine als in he p e-ce amic mix u es, as well as di e en p epa a ion me hods o hei chemical modi ica ions signi - ican ly in luence o al e he esul ing p ope ies o ce amics a e hei sin e ing. Clay Mine als 2024,14, 93 17 o 24 mine als such as alc and kaolini e ep esen he main na u al aw ma e ials o adi ional applica ions mainly o c ea ing silica e ce amics. Silica e ce amics like co die i e, s ea i e, and o s e i e a e used in many indus ial applica ions (especially in elec onics and elec- ical enginee ing) and o e cos sa ings mainly due o using na u al aw ma e ials in compa ison o o he ypes o ce amics. Fu he , silica e ce amics ha e a g ea e sa ili y o applica ions including e ac o y, insula ing, packing ma e ials, il e s, ca alys s, and hick ilms and as glass-ce amics, o s e i e, and bioce amics. Mo eo e , ce amic composi e ma e ials ha e been inc easingly used in a ious ields including ca alys s, sola he mal s o age, and medical applica ions. S ea i e, o s e i e, and co die i e-based ce amics may o e new p ope ies o indus y applica ions. Au ho Con ibu ions: Concep ualiza ion, o ma , esou ces, w i ing, edi ing—A.K. and J.K.; isual- iza ion, in es iga ion—A.K., J.K., D.M. and M.U. All au ho s ha e ead and ag eed o he published e sion o he manusc ip . Funding: This esea ch was unded by Tomas Ba a Uni e si y in Zlin, Facul y o Technology n . IGA/FT/ 2023/008 and IGA/FT/2024/008. Nex , his esea ch was unded by Jan Amos Komensky Ope a ional P og am inanced by he EU and s a e budge o he Czech Republic, no. CZ.02.01.01/00/22_008/0004631. Also, EU unde he REFRESH—p ojec numbe CZ.10.03.01/00/22_003/0000048 ia he Ope a ional P og amme “Jus T ansi ion” unded he p ojec . Da a A ailabili y S a emen : The da a p esen ed in his s udy a e a ailable on eques om he co e- sponding au ho . 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