Graphene or Graphene Derivative Membrane

Abstract

A filtration membrane, suitably for water filtration, comprising a porous substrate layer and an active layer arranged over at least a part of the substrate layer. The active layer has a lamellar structure comprising at least two layers of two-dimensional material. The two-dimensional material comprises graphene or a derivative thereof. There is also provided a method for producing filtration membranes and filtration devices containing the filtration membranes.

Claims

1-53. (canceled)

54. A filtration membrane for water filtration, comprising a porous substrate layer and an active layer arranged over at least a part of the substrate layer, wherein the active layer has a lamellar structure comprising at least two layers of two-dimensional material, and wherein the two-dimensional material is selected from the group consisting of graphene and a derivative thereof, and wherein the substrate is selected from the group consisting of a porous film substrate or a hollow fibre substrate.

55. A filtration membrane according to claim 54, wherein the membrane comprises a porous substrate layer and an active layer arranged over at least a part of the substrate layer, wherein the active layer has a lamellar structure comprising at least two layers of two-dimensional material, and wherein the two-dimensional material is selected from the group consisting of graphene and a derivative thereof; and further wherein the membrane is produced by a method comprising the steps of: a. selecting substrate from a group consisting of a porous film substrate and a hollow fibre substrate; b. optionally, treating the substrate; and c. contacting the substrate with a coating composition comprising the selected graphene or derivative thereof.

56. A membrane according to claim 55, wherein the substrate is formed from a porous film selected from a group consisting of inorganic porous films, organic porous films and inorganic-organic porous films.

57. A membrane according to claim 56, wherein the porous film is formed from materials selected from the group consisting of zeolite, silicon, silica, alumina, zirconia, mullite, bentonite and montmorillonite clay substrate.

58. A membrane according to claim 56, wherein the porous film is formed from materials selected from the group consisting of polyacrylonitrile (PAN), polyamide (PA), Poly(ether) sulfone (PES), cellulose acetate (CA), poly(piperazine-amide), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), poly(phthalazinone ether sulfone ketone) (PPESK), polyamide-urea, poly (ether ether ketone), polypropylene, poly(phthalazinone ether ketone), and thin film composite porous films (TFC).

59. A membrane according to claim 54, wherein the substrate is formed from materials selected from the group consisting of polyamide (PA), polysulphone (PSf), polyvinylidene fluoride (PVDF) and thin film composites (TFC) including polysulphone supported polyamide composite film.

60. A membrane according to claim 54, wherein the substrate is a treated substrate, the surface of the substrate being operable to receive a coating composition has been subjected to hydrophilisation and the addition of at least one functional group selected from the group consisting of hydrophilic additives consisting of hydroxyl, ketone, aldehyde, carboxylic acid and amine groups, and wherein the hydrophilic additives are selected from a group consisting of polyvinyl alcohol, polyethylene glycol, nanofillers, surface modifying macromolecules and zwitterions.

61. A membrane according to claim 54, wherein the substrate has an Rz surface roughness of from 0 to 1 m.

62. A membrane according to claim 54, wherein the substrate has an Rz surface roughness selected from the group of roughness values consisting of <500 nm, <300 nm, <200 nm and <100 nm, <30 nm, <50 nm and <70 nm.

63. A membrane according to claim 54, wherein at least one surface of the substrate is operable to receive the active layer, and further wherein the active layer is hydrophilic.

64. A membrane according to claim 54, wherein the active layer has a thickness of from 2 to 1 m.

65. A membrane according to claim 54, wherein the active layer has a thickness of from 3 to 800 nm or from 4 to 600 nm, such as 5 to 400 nm or 5 to 200 nm, preferably 5 to 150 nm or 5 to 100 nm.

66. A membrane according to claim 54, wherein the graphene or a derivative thereof is selected from the group consisting of graphene oxide, reduced graphene oxide, hydrated graphene, amino-based graphene, alkylamine functionalised graphene oxide, ammonia functionalised graphene oxide, amine functionalised reduced graphene oxide, octadecylamine functionalised reduced graphene oxide and polymer graphene aerogel.

67. A membrane according to claim 66, wherein the selected graphene or derivative thereof is selected from the group consisting of graphene oxide, reduced graphene oxide and amino-group functionalised graphene oxide.

68. A membrane according to claim 66, wherein the selected graphene or derivative is reduced graphene oxide with an oxygen content of from 5 to 20% oxygen atomic percentage.

69. A membrane according to claim 66, wherein the selected graphene or graphene derivative comprises amino groups.

70. A membrane according to claim 69, wherein the selected graphene or graphene derivative comprises grafted amino groups.

71. A membrane according to claim 54, wherein the selected graphene or the graphene derivative is in flake form, wherein the size distribution of the selected graphene flakes or graphene derivative thereof is such that at least 30 wt % of the flakes have a diameter selected from the range of diameters selected from the group consisting of from 1 to 750 nm, from 100 to 500 nm, from 100 to 400 nm, from 100 to 3500 nm, from 200 to 3000 nm, from 300 to 2500 nm, from 400 to 2000 nm, from 500 to 1500 nm, from 500 to 4000 nm, from 500 to 3500 nm, from 500 to 3000 nm, from 750 to 3000 nm, from 1000 to 3000 nm, from 1250 to 2750 nm and from 1500 to 2500 nm.

72. A membrane according to claim 71, wherein the size distribution of the graphene flakes or derivative thereof is selected from the group consisting of size distributions of at least 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt %, 90 wt %, 95 wt %, 98 wt % and 99 wt %.

73. A membrane according to claim 54, wherein the membrane is adapted for a use selected from the use group consisting of water treatment, desalination, oil and water separation, and pharmaceutical filtration.

74. A membrane according to claim 54, wherein the graphene or derivative thereof is formed from a coating composition applied to the substrate, wherein the concentration of graphene or derivative thereof in the coating composition is selected from the group of compositions consisting of from 0.3 mg/ml to 4 mg/ml, from 0.3 mg/ml to 3 mg/ml, from 0.3 mg/ml to 2 mg/ml and from 0.3 to 1.5 mg/ml.

75. A membrane according to claim 74, wherein the viscosity of the coating composition is selected from the group of coating compositions consisting of 1 to 14 cPa, 5 to 15 cPa and 10 to12 cPa.

76. A membrane according to claim 74, wherein the surface tension of the coating composition is selected from the group of surface tensions consisting of from 1 to 150 mN/m and from 28 to 80 mN/m.

77. A membrane according to claim 74, wherein the coating composition has a Z number of between 1 and 16.

78. A method of producing a filtration membrane wherein the membrane comprises a porous substrate layer and an active layer arranged over at least a part of the substrate layer, wherein the active layer has a lamellar structure comprising at least two layers of two-dimensional material, and wherein the two-dimensional material comprises a material selected from the group of materials consisting of graphene and a derivative thereof, the method comprising the steps of: a. selecting a substrate from a group of substrates consisting of a porous film substrate and a hollow fibre substrate; b. optionally, treating the substrate to render it suitable for being coated; and c. contacting the substrate with a coating composition comprising the selected graphene or graphene derivative.

79. A method according to claim 78, and including the step of drying the membrane subsequent to contacting the substrate with the coating composition.

80. A method according to claim 78, and including the step of inkjet printing the coating composition onto the substrate.

Description

EXAMPLES

Example 1Preparation of Graphene Oxide-Containing Filtration Membrane

[0100] A dispersion of graphene oxide was prepared by dispersing 15 g of graphene oxide flakes into 50 L of water using industrial scale sonication, such as using ultrasonic homogeniser sonicator. The resultant dispersion had concentration of 0.3 mg/ml and viscosity of 10.7 cPa. The obtained dispersion was then applied to surface treated polysulfone using a Pixdro LP50 equipped with Xaar 1002 head assembly. Following drying under ambient conditions, the performance of the resultant membrane was then assessed and found to exhibit improvement of water flux by 20% compared to an uncoated membrane.

Example 2Preparation of a Reduced Graphene Oxide Membrane

[0101] A dispersion of reduced graphene oxide was prepared by dispersing 15 g of reduced graphene oxide and Triton X-100 non-ionic surfactant in 50 L water via industrial scale sonication, such as using ultrasonic homogeniser sonicator. The resultant dispersion had a concentration of 0.3 mg/ml and viscosity of 12 cPa. The obtained dispersion was then applied to surface treated polysulfone using a Pixdro LP50 equipped with Xaar 1002 head assembly. Following drying under ambient conditions, the performance of the resultant membrane was then assessed and found to exhibit improvement of selective sieving of organic molecules in comparison to an uncoated membrane.

Example 3Preparation of an Amino-Group Functionalised Graphene Oxide Membrane

[0102] A dispersion of amino-group functionalised graphene oxide was prepared by dispersing 15 g of amino-group functionalised graphene oxide in 50 L water via industrial scale sonication, such as using ultrasonic homogeniser sonicator. The resultant dispersion had a concentration of 0.3 mg/ml and viscosity of 10 cPa. The obtained dispersion was then applied to surface treated polyamide using a Pixdro LP50 equipped with Xaar 1002 head assembly. Following drying under ambient conditions, the performance of the resultant membrane was then assessed and found to exhibit improvement of removal of ferric acid from water in comparison to no removal from an uncoated membrane.

Example 4Preparation of a Filtration Membrane by Flexography

[0103] A dispersion of graphene oxide was prepared by the method detailed in example 1. 975 g of the dispersion was added to 25 g of BASF Joncryl LMV 7050 polymer emulsion and mixed thoroughly using a silverson homogeniser. The viscosity of the liquid coating was then adjusted to the desired print viscosity by addition of water. The liquid coating composition was then applied to a surface treated polysulfone substrate using a RK Printing proofer fitted with a flexo head. Following drying under ambient conditions, the performance of the resultant membrane was assessed and found to exhibit an improvement of 30% of water flux rate versus an uncoated membrane.

Example 5Preparation of a Filtration Membrane by Gravure Printing

[0104] A dispersion of graphene oxide was prepared by the method detailed in example 1. 975 g of the dispersion was added to 25 g of BASF Joncryl LMV 7050 polymer emulsion and mixed thoroughly using a silverson homogeniser. The liquid coating composition was then applied to a surface treated polysulfone substrate using a RK K printing proofer. Following drying under ambient conditions, the performance of the resultant membrane was assessed and found to exhibit an improvement of 25% of water flux rate versus an uncoated membrane.

[0105] Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0106] All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

[0107] Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0108] The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.