Method for manufacture of films and foams

Abstract

The invention relates to a method for the manufacture of films from colloidal suspensions of two-dimensional materials. Specifically, the method involves controlled drying and dispensing of the colloidal suspension on a substrate. The resulting films are freestanding. The invention further relates to the formation of freestanding foams.

1 . A method for making a freestanding film, the method comprising: applying a colloidal suspension of a two-dimensional material to a substrate; and drying the solution to form the film on the substrate. 
     
     
         2 . The method according to  claim 1 , wherein the substrate is a blue steel substrate. 
     
     
         3 . The method according to  claim 2 , wherein the method further comprises removing the freestanding film from the blue steel substrate. 
     
     
         4 . The method according to  claim 1 , wherein the substrate and colloidal suspension is allowed to dry in air for up to 32 hours. 
     
     
         5 . The method according to  claim 1 , wherein the substrate and colloidal suspension are dried using infrared radiation. 
     
     
         6 . The method according to  claim 1 , wherein a bias voltage is applied to the colloidal suspension and/or substrate during dispensing. 
     
     
         7 . The method according to  claim 1 , wherein the two-dimensional material is selected from the group consisting of: group IV materials including graphite, graphite oxide, graphene (C), graphene oxide, graphane (CH), fluorographene (CF), silicene (Si), germanane (GeH), stanene (Sn), borophene (B) and thiophene; MXenes including Ti 3 C 2 , Ti 2 C, Ta 4 C 3 , and Ti 3 (Co.5No.5) 2 ; dichalcogenides including VSe 2 , NbSe 2 , TiS 2 , ZrS 2 , HfS 2 , ReS 2 , PtS 2 , TiSe 2 , ZrSe 2 , HfSe 2 , ReSe 2 , PtSe 2 , SnSe 2 , TiTe 2 , ZrTe 2 , VTe 2 , NbTe 2 , TaTe 2 , MoTe 2 , WTe 2 , CoTe 2 , RhTe 2 , IrTe 2 , NiTe 2 , PdTe 2 , PtTe 2 , SiTe 2 , NbS 2 , TaS 2 , MoS 2 , WS 2 , VS 2 , TaSe 2 , MoSe 2 , WSe 2 , MoTe 2 , SnSe 2 , and SnS 2 ; trichalcogenides including Bi 2 Se 3 , Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 S 3 , In 2 Se 3 , As 2 S 3 , AS 2 Se 3 , NbSe 3 , TiS 3 , ZrS 3 , ZrSe 3 , ZrTe 3 , HfS 3 , HfSe 3 , HfTe 3 , NbS 3 , TaS 3 , and TaSe 3 ; mono-chalcogenides including GeSe, GeTe, GaSe, and GaS; thiophosphates including FePS 3 , MnPS 3 , and NiPS 3 ; oxides including MnO 2 , δ-MnO 2 , MoO 3 , V 2 O 5 , WO 3 , and TiO 2 ; nitrides including BN; oxychlorides including BiOCI, FeOCI, HoOCI, ErOCI, ErOCI, TmOCI, YbOCI, and LnOCI; halides including FeCI 3 , FeBr 3 , CrCI 3 , CrBr 3 , MoCI 3 , MoBr 3 , TiCI 2 , TiBr 3 , InBr 3 , PbCI 2 , AICI 33 , InBr 33 , CrBr 33 , FeCI 2 , MgCI 2 , CoCI 2 , VCI 2 , VBr 2 , VI 2  CdCI 2 , CdOI 2 ; layered silicate minerals including calcium copper silicate (Egyptian Blue); and other materials including CaSi 2 , CaGe 2 , Ca(Si 1-x Ge x ) 2 , Ba 3 Sn 4 As 6 , CaMg 2 N 2 , Caln 2 , CaNi 2 P 2 , CaAuGa, InAs, WS 2 , TiSe 2 , Bi 2 Se 3 , Sb 2 Te 3 , Bi 2 Te 3 , magnesium diboride, TBA x H(1.07 -x )Ti 1.73 O 4 .H 2 O, CoO 2 −, TBA x H( 1-x )Ca 2 Nb 3 O 10 , Bi 2 SrTa 2 O 9 , Cs 4 W 11 O 36   2− , Ni(OH) 5/3 DS 1/3 , Eu(OH) 2.5 (DS) 0.5 , CO 2/3 Fe 1/3 (OH) 2   1/3+  and iron pentacarbonyl. 
     
     
         8 . The method according to  claim 1 , wherein the solution further comprises graphite, graphite oxide, graphene or graphene oxide. 
     
     
         9 . A freestanding film made by the method according to  claim 1 . 
     
     
         10 . A method for making a freestanding foam, the method comprising:
 applying a colloidal suspension of a two-dimensional material to a substrate; and   cooling the colloidal suspension and substrate under vacuum to form the foam on the substrate.   
     
     
         11 . The method according to  claim 10 , wherein the substrate is a blue steel substrate. 
     
     
         12 . The method according to  claim 11 , wherein the method further comprises removing the freestanding foam from the blue steel substrate. 
     
     
         13 . The method according to  claim 10 , wherein the two-dimensional material is selected from the group consisting of:
 group IV materials including graphite, graphite oxide, graphene (C), graphene oxide, graphane (CH), fluorographene (CF), silicene (Si), germanane (GeH), stanene (Sn), borophene (B) and thiophene; MXenes including Ti 3 C 2 , Ti 2 C, Ta4C 3 , and Ti 3 (Co.5No.5) 2 ; dichalcogenides including VSe 2 , NbSe 2 , TiS 2 , ZrS 2 , HfS 2 , ReS 2 , PtS 2 , TiSe 2 , ZrSe 2 , HfSe 2 , ReSe 2 , PtSe 2 , SnSe 2 , TiTe 2 , ZrTe 2 , VTe 2 , NbTe 2 , TaTe 2 , MoTe 2 , WTe 2 , CoTe 2 , RhTe 2 , IrTe 2 , NiTe 2 , PdTe 2 , PtTe 2 , SiTe 2 , NbS 2 , TaS 2 , MoS 2 , WS 2 , VS 2 , TaSe 2 , MoSe 2 , WSe 2 , MoTe 2 , SnSe 2 , and SnS 2 ; trichalcogenides including Bi 2 Se 3 , Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 S 3 , In 2 Se 3 , AS 2 S 3 , As 2 Se 3 , NbSe 3 , TiS 3 , ZrS 3 , ZrSe 3 , ZrTe 3 , HfS 3 , HfSe 3 , HfTe 3 , NbS 3 , TaS 3 , and TaSe 3 ; mono-chalcogenides including GeSe, GeTe, GaSe, and GaS; thiophosphates including FePS 3 , MnPS 3 , and NiPS 3 ; oxides including MnO 2 , 6-MnO 2 , MoO 3 , V 2 O 5 , WO 3 , and TiO 2 ; nitrides including BN; oxychlorides including BiOCI, FeOCI, HoOCI, ErOCI, ErOCI, TmOCI, YbOCI, and LnOCI; halides including FeCI 3 , FeBr 3 , CrCI 3 , CrBr 3 , MoCI 3 , MoBr 3 , TiC 1   2 , TiBr 3 , InBr 3 , PbCl 2 , AlCI 3 3, InBr 3 3, CrBr 3 3, FeCI 2 , MgCI 2 , CoCI 2 , VCI 2 , VBr 2 , VI 2  CdCI 2 , CdCI 2 ; layered silicate minerals including calcium copper silicate (Egyptian Blue); and other materials including CaSi 2 , CaGe 2 , Ca(Si 1-x Ge x ) 2 , Ba 3 Sn 4 As 6 , CaMg 2 N 2 , CaIn 2 , CaNi 2 P 2 , CaAuGa, InAs, WS 2 , TiSe 2 , Bi 2 Se 3 , Sb 2 Te 3 , Bi 2 Te 3 , magnesium diboride, TBA x H( 1.07-x )Ti 1.73 O 4 .H 2 O, CoO 2 —, TBA x H( 1-x )Ca 2 Nb 3 O 10 , Bi 2 SrTa 2 O 9 , Cs 4 W 11 O 36   2− , Ni(OH) 5/3 D 5   1/3 , Eu(OH) 2.5 (DS) 0.5 , CO 2/3 Fe 1/3 (OH ) 2   1/3+  and iron pentacarbonyl.   
     
     
         14 . The method according to  claim 10 , wherein the colloidal suspension and substrate are cooled in stages at about −178.1° C., about −181.0° C., about −190.8° C., about −160.3° C., and about −190.0° C. 
     
     
         15 . A freestanding foam made by the method according to  claim 10 .