US20150104368A1 - Inorganic phosphate compositions and methods - Google Patents
Inorganic phosphate compositions and methods Download PDFInfo
- Publication number
- US20150104368A1 US20150104368A1 US14/512,999 US201414512999A US2015104368A1 US 20150104368 A1 US20150104368 A1 US 20150104368A1 US 201414512999 A US201414512999 A US 201414512999A US 2015104368 A1 US2015104368 A1 US 2015104368A1
- Authority
- US
- United States
- Prior art keywords
- phosphate
- component
- valency
- aggregate
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 229910052816 inorganic phosphate Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 159
- 239000010452 phosphate Substances 0.000 claims abstract description 93
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 79
- 239000007787 solid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims description 112
- 239000011248 coating agent Substances 0.000 claims description 58
- 239000011777 magnesium Substances 0.000 claims description 55
- 239000000919 ceramic Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 45
- 239000007921 spray Substances 0.000 claims description 37
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 34
- 239000000347 magnesium hydroxide Substances 0.000 claims description 33
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 33
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000002829 reductive effect Effects 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 23
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002441 X-ray diffraction Methods 0.000 claims description 19
- 239000000375 suspending agent Substances 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 15
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000006254 rheological additive Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920002907 Guar gum Polymers 0.000 claims description 4
- 229920002310 Welan gum Polymers 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- 229920000591 gum Polymers 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims 1
- 229960002261 magnesium phosphate Drugs 0.000 claims 1
- 235000010994 magnesium phosphates Nutrition 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 37
- 230000002378 acidificating effect Effects 0.000 abstract description 26
- 238000005507 spraying Methods 0.000 abstract description 18
- 235000021317 phosphate Nutrition 0.000 description 76
- 239000002243 precursor Substances 0.000 description 67
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 39
- 229910052749 magnesium Inorganic materials 0.000 description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 30
- 235000012245 magnesium oxide Nutrition 0.000 description 28
- 239000000395 magnesium oxide Substances 0.000 description 27
- -1 polypropylene Polymers 0.000 description 27
- 239000012267 brine Substances 0.000 description 25
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 25
- 239000003973 paint Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000004568 cement Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000010881 fly ash Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 229910052882 wollastonite Inorganic materials 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- 235000010755 mineral Nutrition 0.000 description 14
- 239000010456 wollastonite Substances 0.000 description 14
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 13
- 229910052863 mullite Inorganic materials 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- 239000006072 paste Substances 0.000 description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000003086 colorant Substances 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 10
- 229910000091 aluminium hydride Inorganic materials 0.000 description 10
- 229920006334 epoxy coating Polymers 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000007836 KH2PO4 Substances 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 238000010669 acid-base reaction Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 150000004679 hydroxides Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000011396 hydraulic cement Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000005791 algae growth Effects 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 150000004677 hydrates Chemical class 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 238000000518 rheometry Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000010754 BS 2869 Class F Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 241000195493 Cryptophyta Species 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 235000012241 calcium silicate Nutrition 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 150000002602 lanthanoids Chemical class 0.000 description 4
- YQRTZUSEPDULET-UHFFFAOYSA-K magnesium;potassium;phosphate Chemical compound [Mg+2].[K+].[O-]P([O-])([O-])=O YQRTZUSEPDULET-UHFFFAOYSA-K 0.000 description 4
- 229910052592 oxide mineral Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052604 silicate mineral Inorganic materials 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical group [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229910017736 MH2PO4 Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012223 aqueous fraction Substances 0.000 description 2
- 229960000686 benzalkonium chloride Drugs 0.000 description 2
- 229960001950 benzethonium chloride Drugs 0.000 description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
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- 229960001927 cetylpyridinium chloride Drugs 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- AHYZVKSDOYIXCQ-UHFFFAOYSA-H trimagnesium chloro hypochlorite diphosphate Chemical compound P(=O)([O-])([O-])[O-].O(Cl)Cl.[Mg+2].P(=O)([O-])([O-])[O-].[Mg+2].[Mg+2] AHYZVKSDOYIXCQ-UHFFFAOYSA-H 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/24—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with means, e.g. a container, for supplying liquid or other fluent material to a discharge device
- B05B7/2402—Apparatus to be carried on or by a person, e.g. by hand; Apparatus comprising containers fixed to the discharge device
- B05B7/2472—Apparatus to be carried on or by a person, e.g. by hand; Apparatus comprising containers fixed to the discharge device comprising several containers
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Definitions
- This disclosure relates to multi-component inorganic phosphate formulations of acidic phosphate components and basic oxide/hydroxide components.
- Organic synthetic materials made of epoxy, polyester, polypropylene and other polymers are widely used in composites such as fiber boards, glass fiber composites, sealants for marble and granite countertop surfaces, aircrafts, body armors etc. These resins are relatively expensive, have a high green house gas intensity and are flammable. The volatile organic compounds released by them during their use present a health hazard for a user.
- Phosphate ceramics and ceramics that are made by acid-base reactions between phosphoric acid, or an acid-phosphate, and a metal oxide are generally known.
- the products disclosed in these patents are hard, and replicate properties of either cement or ceramic, or both.
- Rapidly setting compositions such as phosphate ceramics heretofore have proven difficult to spray coat (and atomize) onto surfaces so as to provide a smooth, paint-like finish.
- conventional hydraulic cements can be sputtered coated, but the sputtered coating cannot provide a smooth, paint-like finish as it difficult to obtain good mixing with a high viscosity, unsuspended matrix, and such coatings contain significant amounts of unreacted precursor materials that tend to result in a grainy surface texture.
- mixing a conventional hydraulic cement for extended times in order to improve its homogeneity typically results in the mixture setting before or during spray coating.
- phosphate ceramics are generally translucent after application and set.
- color aggregate in atomizible phosphate ceramics poses challenges.
- Using too small a natural mineral aggregate (e.g., to avoid unwanted texture) in these formulations results in coatings that generally appear white or weakly colored and are therefore not acceptable even at greater than conventional loadings of the colorant.
- Using high loadings of solids and/or larger aggregates in these formulations are generally avoided for rheological difficulties and difficulty atomizing.
- textured, atomizable phosphate ceramic coatings using larger aggregates (including large aggregate colorants such as colored sand aggregates) have heretofore proven difficult to achieve, partly because the larger aggregates can clog the spray/atomizing equipment and the composition must be formulated such that it can hold the large aggregate particles, but at the same time set before the aggregate migrates, for example, down a vertical surface or overhead surface.
- Conventional, non-ceramic paints in contrast, provide too thin a coating to hold large aggregate for texturing and highlighting, at least in part because they have too low a viscosity and because they take too long to set.
- multi-component formulations comprising at least one acidic phosphate first component and at least one alkaline second component, the first and second components being suitable for providing, upon combination, an inorganic phosphate composition.
- One aspect disclosed herein relates to a method for manufacturing chemically stable multi-component inorganic phosphate precursors capable of extended storage and transport.
- a method for modifying inorganic phosphate precursor solutions so as to produce high-strength, rapid-setting phosphate compositions is disclosed.
- inorganic phosphate compositions of low density, reduced crystalline morphology are provided.
- inventions relate to a method for the manufacture of inorganic phosphate compositions for the thermal conversion to materials comprising a berlinite (AlPO 4 ) phase, useful as a fire-resistant coating.
- the aspects disclosed herein include manufacturing methods that use environmentally friendly techniques to provide improved efficiencies in the commercial production of these inorganic phosphate precursors and composition.
- the instant sprayable inorganic phosphate precursor composition comprises aggregate of up to about 30 mesh or larger and can be sprayed at a relatively thin thickness yet still hold the aggregate as well as set fast enough before the aggregate migrates or dislodges from the point of application, e.g., down a wall or from a ceiling surface.
- Such spray coated phosphate ceramic compositions produce high-strength, rapid-setting phosphate ceramic coatings of aesthetically pleasing colors.
- Such compositions can also provide corrosion protection and/or be used as an undercoating in combination with a polymeric coating, such as an acrylic- or urethane-based coating.
- a polymeric coating such as an acrylic- or urethane-based coating.
- said phosphate spray coating compositions are suitable for spray coating on metal surfaces, for example, structural elements and chassis of transportation vehicles such as automobiles, trains, cycles, aerospace vehicles, trucks, and buses.
- the precursor components and compositions disclosed and described herein are based on phosphoric acid or phosphate salt solutions. Certain embodiments employ sparsely-soluble oxides and sparsely-soluble oxide minerals, which are oxides and oxide minerals that have limited solubility in water at neutral pH.
- the precursor components comprise at least one acidic phosphate component (first component) and at least one basic oxide/hydroxide component (the second component).
- the first component is prepared as an aqueous solution of phosphoric acid or phosphate salts such that the solution has a pH of about 1.5 to about 5. In one aspect, aqueous solutions comprising the first component having pH below 1.5 and/or above 5 are excluded.
- the second component is prepared by the slow addition of the sparsely-soluble oxides, or the sparsely-soluble oxide minerals to an aqueous solution of pH of 9-14.
- the sparsely-soluble oxide, or sparsely-soluble hydroxide are provided as a component of a brine solution derived from a natural source and optionally modified so as to provide an effective amount of the sparsely-soluble oxide in the form of its hydroxide.
- a brine solution derived from a natural source
- magnesium brine comprising an effective amount of magnesium hydroxide, optionally with effective amounts of chlorides, oxychloride, sulphates, and oxysulphates is used.
- the use of such liquid sources of the sparsely-soluble oxide in the form of its hydroxide allows for the elimination or reduction of problems associated with the good wetting of individual grains of powders typically employed in the preparation of inorganic phosphate materials, and avoids or reduces any excessively exothermic reactions.
- the resulting inorganic phosphate compositions prepared from the aforementioned first and second precursor components has a unique morphological structure.
- the instantly mixed formulation or the set product can be used as a thin/thick coating, paint, instant adhesive, or as a matrix for composites, or as anti-corrosion or fire resistant coating for use on metal and non-metal structural materials.
- the first component and the second component are combined together to provide an inorganic phosphate composition.
- aggregate colorants can be added of a size and of an amount so as to impart a visible color to the set product.
- the pH of the first component is adjusted to between about 2.5 to about 5, or between about 3 to about 4.5.
- the first component comprises phosphoric acid, a dihydrogen phosphate salt of formula M m (H 2 PO 4 ) m and its hydrates, or mixtures thereof; where M sodium, potassium, magnesium, calcium, aluminum, or mixtures thereof, and m is 1-3.
- the first component comprises at least two of an alkali dihydrogen phosphate M(H 2 PO 4 ) or its hydrate, phosphoric acid, an alkali earth dihydrogen phosphate M(H 2 PO 4 ) 2 or its hydrate, or a trivalent metal trihydrogen phosphate MH 3 (PO 4 ) 2 or its hydrate.
- the first component comprises a metal hydrophosphate represented by the formula M 3 (PO 4 ) 2 and its hydrates, where M is aluminum (III), iron (III), manganese (III), lanthanides selected from lanthanum (III), cerium (III), yttrium (III), scandium (III), and mixtures thereof.
- M aluminum (III), iron (III), manganese (III), lanthanides selected from lanthanum (III), cerium (III), yttrium (III), scandium (III), and mixtures thereof.
- the first component comprises mono potassium phosphate or its hydrate, in combination with one or more of phosphoric acid or aluminum trihydrogen phosphate or its hydrate such that the pH of the solution is between 2-5.
- A is sodium, potassium, cesium, iron (II), iron (III), magnesium (II), zinc (II), aluminum (III), bismuth (III), zirconium (IV) or mixtures thereof.
- the first component comprises phosphoric acid, alkali metal dihydrogen phosphate MH 2 PO 4 , alkali earth dihydrogen phosphate M(H 2 PO 4 ) 2 or its hydrate, transition metal trihydrogen phosphate MH 3 (PO 4 ) 2 or its hydrate, or mixtures thereof, in combination with an alkali metal oxide, alkali metal hydroxide, alkali earth metal oxide, or a basic mineral.
- the pH of the second component is adjusted to between about 9 to about 13 or between about 10 to about 12, or between about 10 to about 11.
- the second component comprises an oxide represented by the formula BO, or a hydroxide represented by the formula B(OH), where B is an alkali earth metal or transition metal.
- B may be sodium, potassium, magnesium, calcium, zinc, barium, aluminum, yttrium, a lanthanide, zirconium, iron, bismuth or manganese.
- the second component may be an oxide or hydroxide of: magnesium, barium calcium, zinc, iron(II), manganese (II), or mixtures thereof.
- the second component is magnesium brine having a pH of about 9 to about 11, or about 10 to 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide.
- the magnesium hydroxide may be characterized by having a hexagonal platelet morphology.
- the magnesium brine may further contain an effective amount of magnesium hydroxide, magnesium chloride, magnesium sulphate, magnesium oxychloride precursor, magnesium oxysulphate precursor, or mixtures thereof.
- the second component comprises particulate matter having an average minimum surface area of greater than 5 m 2 /g.
- the second component further comprises wollastonite, talc, fly ash, kaolin clay, kaolinite, meta kaolin, mullite, calcium aluminate minerals, calcium silicate minerals, aluminum silicate minerals, calcium aluminum silicate minerals, or mixtures thereof, in a weight ratio of between 1:0.05 to 1:6 of the second component.
- the first component is mono potassium phosphate or its hydrate
- the second component is magnesium brine having a pH of about 9 to about 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide.
- the first component is mono potassium phosphate or its hydrate
- the second component is magnesium brine having a pH of about 9 to about 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide, magnesium chloride, magnesium sulphate, magnesium oxychloride phosphate precursor, magnesium oxysulphate phosphate precursor, or mixtures thereof.
- the first component comprises Mg(H 2 PO 4 ) 2 or its hydrate
- the second component comprises an alkali metal oxide or alkali metal hydroxide.
- the first component comprises AlH 3 (PO 4 ) 2 or its hydrate
- the second component comprises an alkali metal oxide or alkali metal hydroxide.
- the resultant reaction product is of reduced crystalline morphology or reduced nucleation centers.
- the first component or the second component has an average particle size of less than 50 micron.
- the second component is alkali earth metal oxy-chloride phosphate precursors, alkali earth metal oxy-sulfate phosphate precursors, or mixtures thereof.
- the second component further comprises fillers wollastonite (CaSiO 3 ), talc (Mg 3 Si 4 O 10 (OH) 2 , mullite (alumino silicate), both Class C fly ash and Class F fly ash, the reactive filler present in a weight ratio of 1:0.5 to 1:6 to the second component.
- a product prepared by the process as defined in the first embodiment is provided.
- an inorganic phosphate compound is provided.
- the density of the inorganic phosphate is less than 1.8 g/cm 3 or less than 1.5 g/cm 3 .
- the compound is Na 2 KPO 4 . NaK 2 PO 4 . MgKPO 4 . Mg(ZnPO 4 ) 2 . Mg(K 2 PO 4 ) 2 . Mg 2 KPO 4 . Mg(ZnPO 4 ) 2 . Mg(K 2 PO 4 ) 2 . AlK 3 (PO 4 ) 2 . Al 2 Mg 3 (PO 4 ) 2 . ZrOKPO 4 . Mg(ZrOPO 4 ) 2 . Zr(OH) 2 KPO 4 . or Mg[Zr(OH) 2 PO 4 ) 2 ] 2 .
- providing a second component comprising a solution of an alkaline oxide or alkaline hydroxide represented by B 2m
- M is zirconium (IV).
- the pH is adjusted to between 2-5 or the pH is adjusted to between 3-4.5, or the pH is adjusted to between 3-3.5.
- the first component comprises magnesium oxychloride, magnesium oxysulfate, or mixtures thereof, in combination with an amount of hydrochloric acid or sulfuric acid to reduce the pH to between 2 to 5.
- a product prepared by the process as defined in the third embodiment is provided.
- the second component comprises zirconium compounds, zinc compounds, or mixtures present in an amount of between 0-5 wt. % of the second component.
- a method of producing berlinite comprises: providing a first component comprising aluminum trihydrogen phosphate AlH 3 (PO 4 ) 2 . or its hydrates; providing a second component comprising aluminum hydroxide; combining the first component and the second component together; and heating the combination at an elevated temperature sufficient to form a berlinite phase (AlPO 4 ) detectable by x-ray diffraction.
- a method of producing a high-temperature resistant coating comprises: providing a first component comprising aluminum trihydrogen phosphate AlH 3 (PO 4 ) 2 . or its hydrates; providing a second component comprising aluminum hydroxide; combining the first component and the second component together; and contacting a surface of an article with the combination of the first component and the second component; heating the surface of the article at an elevated temperature sufficient to form a coating comprising a berlinite phase (AlPO 4 ) detectable by x-ray diffraction.
- a method of producing aluminum trihydrogen phosphate (AlH 3 (PO 4 ) 2 . or its hydrates comprises heating a solution comprising at least one of aluminum oxide or aluminum hydroxide or aluminum oxide hydrate, and phosphoric acid to an elevated temperature for a time sufficient to dissolve to a maximum amount the at least one of aluminum oxide or aluminum hydroxide or aluminum oxide hydrate; and cooling to form a viscous solution.
- the method further comprises adding about 0.5 wt. % to about 2 wt. % of a source of fluoride ion to the solution.
- the method further comprising adding about 0.2 wt. % to about 1 wt. % of an oxidizer to the solution.
- the oxidizer is selected from potassium permanganate, potassium chromate, sodium chromate, a soluble nitrate of potassium, magnesium, or aluminum.
- the method further comprises combining with the viscous solution at least one of magnesium brine, magnesium hydroxide or magnesium oxide to form a reactive mixture; and applying the reactive mixture on a substrate.
- aggregate material is present in an amount in at least one of the first and the second component capable of imparting an observable color and/or texture.
- the first component can comprise mono potassium phosphate or its hydrate, in combination with one or more of phosphoric acid or aluminum trihydrogen phosphate or its hydrate such that the pH of the solution is between 2-5.
- the first component can comprise mono calcium phosphate or its hydrate.
- the first component, A can be sodium, potassium, cesium, iron (II), iron (III), magnesium (II), zinc (II), aluminum (III), bismuth (III), zirconium (IV) or mixtures thereof.
- the first component preferably comprises phosphoric acid, alkali metal dihydrogen phosphate MH2PO4, alkali earth dihydrogen phosphate M(H2PO4)2 or its hydrate, transition metal trihydrogen phosphate MH3(PO4)2 or its hydrate, or mixtures thereof.
- the second component can be an oxide represented by the formula BO, or a hydroxide represented by the formula B(OH)2, where B is an alkali earth metal or transition metal, wherein B is sodium, potassium, magnesium, calcium, zinc, barium, aluminum, yttrium, a lanthanide, zirconium, iron, bismuth or manganese.
- the second component can be an oxide or hydroxide of magnesium, barium calcium, zinc, iron(II), manganese(II), or mixtures thereof.
- the second component can be magnesium brine having a pH of about 9 to about 11.
- the phosphate ceramic spray composition can further comprise aluminum oxide present in an amount sufficient to increase the hardness of the phosphate ceramic. Solids content of up to about 75 wt % for either the first or second component can be used.
- the rheology modifer/suspending agent is at least one of guar gum, diutan gum, welan gum, and xanthan gum.
- the aggregate is present in an amount of at least about 1 wt % to about 60 wt %.
- the aggregate is at least one of a resin coated silica and a naturally colored mineral aggregate. The aggregate can be of an average particle size of about 20 mesh micron to about 400 mesh.
- the aggregate is of an average particle size of at least about 20 mesh or less and, after application of a coating of less than about 20 mil, the sprayed phosphate ceramic coating substantially retains the aggregate in the coating on a vertical surface or an overhead surface.
- the first and second components can be as described above for the seventh embodiment.
- aggregate material can be present in an amount in at least one of the first and the second component capable of imparting an observable color and/or texture.
- the step of atomizing comprises urging the first component and the second component through an atomizing orifice using at least one of a multi-channel pump, a plural piston pump, peristaltic pump, a ram discharge extruder, and a progressive cavity pump.
- the step of atomizing further comprises a mixer configured to mix the first component, the second component, and the aggregate. In combination with any of the previous aspects of the eighth embodiment, the step of atomizing comprises dispensing the first and second components essentially simultaneously.
- the rheology modifer/suspending agent is at least one of guar gum, diutan gum, welan gum, and xanthan gum.
- the aggregate is present in an amount of at least about 1 wt % to about 60 wt %.
- the aggregate can be of an average particle size of about 20 mesh to about 400 mesh.
- the aggregate can be at least one of an aggregate colorant comprising a naturally colored mineral aggregate and an aggregate colorant comprising resin coated silica.
- the aggregate is of an average particle size providing surface texture to the spray composition after application.
- the method further comprises the step of forming a coating of less than about 20 mil thickness and retaining the aggregate in the coating when applied to a vertical surface or overhead surface, wherein the aggregate is at least 400 mesh.
- FIG. 1 Depicts an X-ray diffraction pattern of a thin coating (blue) and thick coating of magnesium potassium phosphate composition as disclosed and described herein.
- FIG. 2 Depicts an X-ray diffraction pattern of a conventional Ceramicrete (a phosphate cement).
- FIG. 3 Depicts an X-ray diffraction pattern of alumophosphate (AlH 3 (PO 4 ) 2 .2.5H 2 O) A, and Al(OH) 3 as disclosed and described herein, evidencing a reduced crystalline or amorphous phase.
- AlH 3 (PO 4 ) 2 .2.5H 2 O alumophosphate
- Al(OH) 3 Al(OH) 3 as disclosed and described herein, evidencing a reduced crystalline or amorphous phase.
- FIG. 4 Is a photograph of an aluminum hydrophosphate gel as disclosed and described herein.
- FIG. 5 Depicts an X-ray diffraction pattern of a coating produced from aluminum hydro phosphate, wollastonite, and magnesium oxide as disclosed and described herein.
- FIG. 6 Depicts an X-ray diffraction pattern of an alumophosphate, MgO and mullite sample disclosed and described herein compared with pure mullite and alumophosphate are shown for comparison.
- FIG. 7 Depicts coatings produced by using aluminum hydro phosphate and magnesium oxide precursor materials as disclosed and described herein.
- a multi-component formulation comprising at least one acidic component and at least one alkaline component. Both components of the multi-component formulation are provided as solutions, emulsions, dispersions, pastes, or combinations thereof. Each of the components are produced separately and stored separately, and may be dispensed separately or in combination. The components ultimately are combined prior to or during application and are allowed to react to form an inorganic phosphate composition.
- the resultant reaction products of the multi-component formulation are near neutral in pH and may provide refractory-like compositions that are stable at very high temperature, for example, exceeding 2000° F., e.g., temperatures where most of the commercial organic-based products and some inorganic produces can not survive.
- the above formulations are provided as suitable coatings and/or paints and are formulated for high solids spray coating.
- conventional spray coating of hydraulic cements Using spray equipment with aggregate-containing formulations as conventional paint/coating formulations has been problematic for a number of reasons, some of which include the difficulty of passing larger-sized aggregates through small orifices of spray equipment and even more so, the difficulty of keeping such aggregates from migrating once they are sprayed on a surface.
- the ability to atomize such aggregate-containing formulations and obtaining acceptable coated surfaces has been elusive. Decreasing the set time of the formulation provides only a partial solution to this problem and is generally inapplicable for conventional paints.
- ceramic formulations that are capable of spray coating, as well as capable of atomization so as to provide a “paint-like” appearance.
- the instant formulations can be directly sprayed on surfaces, e.g., metal surfaces, concrete surfaces, and other structural surfaces, but in contrast, the instant formulations provide functional, value-added properties at a level not possible from conventional paints, such as metal corrosion protection and fire resistance.
- paint-like final coatings of ceramics are provided using conventional spray equipment. It is further been demonstrated that aggregate colorants can be effectively incorporated into the already high-solids formulation components so as to provide colored coatings. It has also been demonstrated to provide textured surfaces of the instant formulations using aggregates of larger size, e.g., sand.
- a rheology modifer/suspending agent in an amount capable of providing shear thinning of either the first component or the second component and further capable of suspending a high solids content of either the first component or the second component for atomization, excellent paint-like coatings are obtained.
- a sprayable ceramic coating comprises a first component and a second component, a suspension agent, aggregates of particle size of less than about 30 mesh, and a rheology modifier.
- A may also be a reduced oxide phase when higher-valent oxides are used.
- A can be the metal of lower oxidation state.
- n can be any number, normally ranging from 0 to 25.
- hydro phosphates of trivalent metals such as aluminum, iron and manganese represented by the formula AH 3 (PO 4 ) 2 .nH 2 O, where A is a transition metal that includes aluminum, iron, manganese, yttrium, scandium, and all lanthanides such as lanthanum, cerium, etc.
- phosphoric acid may be added and the pH may be adjusted to bring down the pH.
- a preferred pH selected is between 3 and 4, and the most preferred pH is between 3 and 3.5.
- elevating the pH of phosphoric acid or that of an acid-phosphate such as magnesium dihydrogen phosphate (Mg(H 2 PO 4 ) 2 ) or aluminum trihydrogen phosphate (AlH 3 (PO 4 ) 2 ) by neutralizing partially using an alkaline oxide, hydroxide, or a mineral, or by acidifying a dihydrogen phosphate such as mono potassium phosphate (KH 2 PO 4 ) that has a pH greater than 3.5 by adding a small but appropriate amount of phosphoric acid or a low pH acid phosphate such as Mg(H 2 PO 4 ) 2 or aluminum trihydrogen phosphate AlH 3 (PO 4 ) 2 . Examples described later in this document provide the art of adjusting this pH.
- the acid-phosphate used in the precursor is only partially soluble.
- the precursor is milled so that the average particle size passes through 230 mesh sieve (less than 70 micron).
- the acidic component consists of magnesium oxychloride, and magnesium oxysulfates appropriately acidified with either hydrochloric acid or sulfuric acid to reduce the pH.
- Water may be added to the precursor component to reduce the viscosity thereof, or other types of viscosity reducing agents may be used. Commercial additives that prevent algae growth may also be added to this precursor so that no algae growth occurs during storage of this precursor.
- the basic precursor generally consists of a sparsely soluble oxide, or preferably a hydroxide with an average particle size less than 70 micron.
- Mg(OH) 2 magnesium hydroxide
- Mg(OH) 2 reacts with an acid-phosphate instantly resulting in two favorable consequences.
- the crystalline growth cannot occur due to very short time of reaction.
- solubility of Mg(OH) 2 is much higher than that of calcined MgO, most of it dissolves and hence there will not be many nucleation centers for any crystalline growth of the reaction product. The net result is a greater amorphous structure.
- the use of uncalcined oxides or hydroxides as basic precursors to produce substantially reduced crystalline inorganic phosphate compositions as herein disclosed and described provides a major distinction and a substantial improvement over conventional phosphate ceramics.
- the use of calcined oxides can provide for improved coloring of the set coating over the uncalcined oxides or hydroxides.
- Calcining oxides is a major source of energy consumption in acid-base cements and coatings. This can be eliminated by using uncalcined oxides and hydroxides.
- a brine of Mg(OH) 2 obtained directly from magnesia mines provides for a suitable source of the first component alone or in combination with other basic minerals or filler.
- the brine contains at least about 60% dissolved, suspended or dispersed Mg(OH) 2 and can be used directly to provide the second alkaline component of the inorganic phosphate composition.
- a two part component system is provide, one part is an acidic phosphate precursor component whose pH lies between 2-5, 2.5-4.5 in a preferred range, and 3-4.5 range in the most preferred range.
- a basic precursor component having a pH range from 9-14, a preferred range of 10.5-12, and 11-12 in the most preferred range.
- the first compound on the right hand side of Eq. (1) is the acid phosphate precursor material, which may be a hydrate.
- the second compound is the base precursor material, which may also be a hydrate.
- the acid-base reaction that produces the inorganic phosphate composition for the example discussed above is given by equation (3):
- Mg(OH) 2 may be used as a very fine powder passing—less than 70 micron (mesh 230-235). It may be reacted with an acid-phosphate that exhibits a pH greater than 3. For example, one may use mono potassium phosphate solution, whose pH is 4.2, and bring down its pH by adding small amount of phosphoric acid or a di hydrogen phosphate of very low pH, such as aluminum di-hydrogen phosphate (AH 3 (PO 4 ) 2 .nH 2 O)., whose pH is approximately 1.2.
- Use of Mg(OH) 2 reduces the energy consumption in the life cycle cost of the product and hence also reduces green house gas release in the entire process.
- the inorganic phosphate composition is formed by combining the first and second precursor components. Suitability and proportion of these components and their compatibility is governed by the stoichiometry of the acid-base reaction. Table 1 summarizes these combinations, and the chemical formulae for the resulting inorganic phosphate compositions.
- the water which is either added to initiate the reaction, or is the water formed during reaction, may be present as free or bound water.
- Table 1 does not distinguish between the two, but that distinction is of little consequence because the free water will evaporate when the product is dried, but the bound water will remain in the structure.
- Amount of the bound water may be estimated by using conventional analytical tools and techniques, such as differential scanning calorimetry, for example.
- B has a valency
- examples of monovalent elements are sodium (Na), potassium (K), or ammonium (NH 4 ).
- major divalent elements one may use are magnesium, calcium, zinc, barium etc., while trivalent elements are aluminum, iron etc., and an example of quadrivalent element is zirconium (Zr).
- Other elements may be used that fit into the combinations given above and the disclosure and claims are should not to be limited by the examples given above.
- the stoichiometry dictates the composition of the adhesive, it is not possible to exactly tailor that composition in a production process.
- the basic oxide and hydroxide precursor content is kept at a stoichiometric higher amount compared to the acid-phosphate precursor content. This provides a product that is substantially free of any residual acid.
- Cements and ceramics may generally be produced by using acidic phosphate and oxides and oxide minerals. These cements and ceramics are typically formed by mixing an acid-phosphate and the solid oxide in water. This mixture is used immediately and ultimately sets into a solid product within hours. These formulations of precursors and the overall process, however, is not useful for producing formulations suitable for dispensing, for example, as thin film coatings and the like. At least some of the reasons for this include, for example: such compositions are rapid-setting cements containing particulate matter; and maximum working times after combining and before setting is only couple of hours. Thus, they do not have a shelf life needed for paints and coatings. To produce a smooth, thin coating, it is typically necessary to use very fine particles as components.
- an exothermic acid-base reaction releases heat and heats the reacting mixture, which may help setting.
- a significant amount of this exothermic heat is dissipated due to the large surface area of a relatively thin coat.
- the acid-base precursor media is atomized; the atomization cools the media by several degrees which inhibits the acid-base reaction on the surface of the substrate. This leads to dripping (or rebound) of unreacted media from vertical/overhead surface such as walls/ceilings, and also gives efflorescence on the dried surface.
- the compositions of paints and coatings need to be tailored to instant reaction that produces higher amount of exothermic heat that will harden the sprayed product. This is another reason, why large surface area of particles is needed for conventional cements.
- Dispensing of the components may be done using conventional dispensing equipment, such as for example, a dual source extruder, rams, pumps etc. fitted with a suitable spray gun, optionally with an in-line static mixer.
- the spray equipment excludes texture guns as they typically are used for hydraulic cement dispensing/sputtering.
- a multi-component formulation that provides at least one or more of the following properties prior to combining the respective components, or after combining: providing viscosities of the individual components less than about 35,000 centipoise in general, preferably less than about 15,000 centipoise; bonding/adhering to a substrate, the individual components when dispensed, or within a short time thereafter so that they are not adversely affected by exposure to different atmospheric conditions such as rain, sun, and wind; bonding to the substrate a hard and dense set coating that meets standards designed for a particular application such as fire protection, corrosion resistance, chemical resistance, architectural appeal, etc.; exhibit long term durability against the entire solar spectrum, and heat and cooling cycles for the set coating; providing a pH greater than about 2 for the acidic phosphate precursor component and a pH of less than about 12 for the basic precursor component to avoid occupational hazard and to protect environments during any use, disposal or spill; providing essentially homogeneous components during storage, and segregation of water not occurring
- the components can be re-mixed easily prior to application back into a homogenous state; minimizing the tendency of the basic precursor to harden by pozzalinic reaction during storage for at least six months; and/or preventing bioactivity of the acidic precursor.
- the coatings prepared as disclosed here are durable, are not deteriorated by ultra violet radiation, and certain formulations are reflective to infra red radiation and, hence, support energy conservation in a building.
- the disclosed compositions are suitable for primers and top coats as they provide excellent bonding to a variety of substrates.
- a suitable applicator system is needed.
- a plural system in which the acid and base precursor materials can be stored separately in the proportion desired, and then can be dispensed.
- the inorganic phosphate composition precursors can be introduced in a mixing chamber during application or mixed upon exiting a spray device.
- Such systems are common in the market, and can be adapted for dispensing acidic and/or alkaline components without deteriorating the inner surface or components of the device.
- the viscosity of the two components should be sufficiently low so that dispensing is facilitated. Generally, either precursor viscosity of less than 35,000 centipoise (cp) or less is acceptable for many pumps, but a viscosity of less than 15,000 cp is preferable.
- the viscosity depends on the amount of powder material in the solution.
- the oxide powders or the mineral powders used in the solution have to be very fine in nature and are ground to pass ⁇ 325 micron sieve size.
- Brine of Mg(OH) 2 is ideal for this purpose because it exhibits a low viscosity and hence no processing of brine is needed.
- the viscosity of the second component may be adjusted by adding partially reactive minerals such as wollastonite (calcium silicate, CaSiO 3 ), or mineral containing materials such as fly ash.
- partially reactive minerals such as wollastonite (calcium silicate, CaSiO 3 ), or mineral containing materials such as fly ash.
- Class F fly ash is preferred because the small amount of carbon acts as a lubricant on particles and helps reduce the viscosity of the precursor components.
- the content of the additive may range from an amount equal to the second precursor component to twice that. If other oxides are used, the amount may be adjusted correspondingly to obtain a viscosity less than 15,000 cp.
- viscosity may also be adjusted by adding commercial waterbourne paint conditioners in a small quantity, which can adjust (e.g., reduce) the viscosity as needed.
- both the acidic and alkaline precursor components should have good shelf life, preferably greater than 6 months, greater than one year, or greater than 18 months.
- shelf life preferably greater than 6 months, greater than one year, or greater than 18 months.
- alkaline oxide components tend to undergo pozzalinic reactions (reaction that occurs in Portland cement or in wet fly ash), in the presence of moisture such that the alkaline powder sets by itself into a hard mass resulting in difficulty reconstituting and/or grinding the hardened mass for use.
- an alkaline precursor component may comprise wollastonite and Class F fly ash in an amount not to exceed more than three times that of the Mg(OH) 2 or any oxide in the broadest range and two times in the specific range to provide a reasonably good shelf life.
- compositions optionally may include one or more additives, such as fillers surfactants (anionic or cationic, amphoteric, or nonionic), plasticizers, settling agents, rheology modifiers and/or suspending agents, and/or anti-foamers.
- additives such as fillers surfactants (anionic or cationic, amphoteric, or nonionic), plasticizers, settling agents, rheology modifiers and/or suspending agents, and/or anti-foamers.
- Suitable fillers include for example, wollastonite, talc, Class C or F fly ash, kaolin clay, kaolinite, meta kaolin, mullite, calcium aluminate minerals, calcium silicate minerals, aluminum silicate minerals, calcium aluminum silicate minerals, or mixtures thereof. Other fillers alone or in combination with the above may be used. In certain aspects, the weight ratio of the filler is between 1:0.05 to 1:6 to that of the second component. In certain aspects, the instant compositions can be essentially free of calcium silicates.
- Suitable anionic surfactants include, for example, perfluorooctanoate (PFOA or PFO), perfluorooctanesulfonate (PFOS), sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, alkyl sulfate salts, sodium lauryl ether sulfate (SLES), alkyl benzene sulfonate, and soaps or fatty acid salts.
- PFOA or PFO perfluorooctanoate
- PFOS perfluorooctanesulfonate
- SDS sodium dodecyl sulfate
- ammonium lauryl sulfate alkyl sulfate salts
- sodium lauryl ether sulfate SLES
- alkyl benzene sulfonate sodium lauryl ether sulfate
- Suitable cationic surfactants include, for example, cetyl trimethylammonium bromide (CTAB), alkyl timethylammonium salt, cetylpyridinium chloride (CPC), polyethoxylated tallow amine (POEA), benzalkonium chloride (BAC), and benzethonium chloride (BZT).
- Suitable amphoteric surfactants include, for example, dodecyl betaine, cocamidopropyl betaine, and coco ampho glycinate.
- Suitable nonionic surfactants include, for example, alkyl poly(ethylene oxide), alkylphenol poly(ethylene oxide), poloxamers or poloxamines (copolymer of polyethylene oxide or polypropylene oxide), octyl glucoside, decyl maltoside, cetyl alcohol, oleyl alcohol, and dodecyl dimethylamine oxide.
- Other surfactants alone or in combination with the above may be used.
- Suitable plasticizers include, for example phthalates, trimellitates, aliphatic dibasic esters, phosphates, epoxides, or polyesters.
- Specific examples of plastizers include, for example, DOP (di(2-ethylhexyl) phthalate, DINP (di(isononyl) phthalate, TOTM (tris(2-ethylhexyl)trimellitate, TINTM (tris(isononyl)trimellitate, DOA (di(2-ethylhexyl) adipate, DINA (di(isononyl) adipate, DOZ (di(2-ethylhexyl) azelate, and DOS (di(2-ethylhexyl) sebacate.
- Other plastizers alone or in combination with the above may be used.
- Anti settling agents include, for example, soya-lacithin, aluminium stearate, stearate coated calcium carbonate, modified cater oil or fatty acids, dipentene, pine oil, methyl ethyl ketoxime, di-isobutylene-maleic dispersion, ammonium polyacrylate, modified soya lecithin emulsion, polycaprolactonepolyol-polyethyleneimine block copolymer, polycaprolactonepolyol-toluene diisocynate copolymer, polyhydroxystearic acid, and alkyd based anti settling agents. Other settling agents alone or in combination with the above may be used.
- Suitable rheology modifiers/suspending agents include hydrated magnesium aluminum silicate, lignosulfonates (calcium lignosulfonates, sodium lignosulfonates and the like), salts of sulfonated naphthalene sulfonate condensates, salts of sulfonated melamine sulfonate condensates, beta naphthalene sulfonates, sulfonated melamine formaldehyde condensates, naphthalene sulfonate formaldehyde condensate resins, for example, LOMAR D® dispersant (Cognis Inc., Cincinnati, Ohio), polyaspartates, oligomeric dispersants, polymethacrylate salts, guar gum, diutan gum, welan gum, xanthan gum and/or other agents that function as a rheology modifiers/suspending agent.
- lignosulfonates calcium
- rheology modifiers/suspending agents for example, DARVAN (sodium polymethacrylate) can provide only limited performance, e.g., providing smooth coatings at only about 15% of Al2O3 or other similar high density particles.
- DARVAN sodium polymethacrylate
- Anti-foamers include, for example, silicon based anti-foam oil (siloxane with polyether terminal groups), acetylene glycol surfactants, and poly octyl acrylates. Other anti-foamers alone or in combination with the above may be used.
- Phosphates are nutrients for algae and hence one should expect algae growth in the acidic component.
- various commercial additives that inhibit any biological activity.
- One good example is cupric oxide.
- the addition of less than 1 wt. % of cupric oxide in the acidic phosphate precursor is sufficient to inhibit biological growth.
- Other commercial chemicals used to prevent algae or fungal growth may also be used.
- novel inorganic two component precursor formulations comprising acid phosphates, oxychloride, and oxysulfate solutions and pastes, and a basic component comprising oxides and hydroxides, that can be brought together to react instantly so that the resulting product is an inorganic (oxychloro-) or (oxysulfo-)phosphate composition.
- Methods of producing the two acid and base components and their combinations, atomizable sprayable formulations, and optionally a substantially amorphous, reduced crystallinity ceramic are disclosed and characterized as set forth in the following selected examples, but the methods and claims are also applicable to other acid-base formulations with suitable modification of the components such as oxychloride and oxysufate systems. A brief discussion on these modifications is provided, but that discussion is not intended to limit the claims or the disclosure itself.
- the first (acidic) component consisted of mono potassium phosphate (MKP) having a pH of about 4.2 when measured in aqueous solution.
- MKP mono potassium phosphate
- the MPK was then further milled for an hour and Its pH was adjusted between 3.2 and 3.5 by adding 2.5 wt. % phosphoric acid (added as 50% dilute solution).
- 0.5 wt. % cupric oxide was added to prevent algae growth.
- the solution was adjusted with water to yield a viscosity of approximately 10,000 centipoise.
- the density of this component was 1.9 g/cm 3 .
- the second component (alkaline) was prepared as follows: A requisite amount of magnesium brine solution (Martin Marietta), as a source of magnesium hydroxide, was weighed into a mixer. Zr(OH) 4 powder was added to the brine and stirred for 5-10 min until homogenous. Wollastonite passing 325 mesh was added slowly to this solution and mixed for 10-15 min. An additional amount of water was added to adjust the viscosity to approximately 20,000 to 25,000 centipoise. The density of this liquid component was 1.25 g/cm 3 and the average particle size of particles in this solution was determined to be about 5.6 micrometers or less. Thus, the second component consisted of about 69 wt. % magnesium brine (providing about 61 wt. % Mg(OH) 2 ), about 8.7 wt. % wollastonite, about 2.2 wt. % zirconium hydroxide (Zr(OH) 4 ), the remainder water.
- the two components were combined in the volume ratio of 1:1 for spray using a plural spray system.
- the two cartridges of the spray system were filled separately with the two components.
- the spray gun consisted of a mixing tube, in which the two components could be mixed prior to spraying.
- the composition was sprayed on different substrates e.g., steel, wood, hardboard, aluminum, concrete, mild steel Taber panels. The thickness coated was approximately 15-20 mil. Abrasion resistance measurements were made according to ASTM D 4060. The coatings were allowed to cure at ambient conditions for 7 days before all tests and sample analyses were done.
- the density of the inorganic phosphate composition disclosed herein is less than that of Ceramicrete, which is believed due to more complete reaction of magnesium hydroxide source and the reduced amount of particulate magnesium oxides.
- the inorganic phosphate compositions disclosed and described herein result in lower density materials, for example, densities of about 1.4 g/cm 3 , which are comparable to organic coatings.
- densities of typical organic phosphate cements of similar composition prepared from periclase are between 1.8 to 2.0 g/cm 3 .
- Magnesium hydroxide has a hexagonal platelet or sheet structure that is structurally and morphologically different from calcined magnesium oxide (periclase) that has a cubic structure.
- calcined magnesium oxide periclase
- the sheet structure of magnesium hydroxide resultant inorganic phosphate compositions derived therefrom provide smoother coatings and superior abrasion resistance compared to coatings prepared from calcined magnesium oxide derived inorganic phosphates.
- the average particle size difference of the resultant inorganic phosphate compositions derived from magnesium hydroxide (greater than 5 m 2 /g) as disclosed and described herein also contributes to the superior abrasion resistance and smoothness of the coatings verses those of calcined magnesium oxide (less than 0.55 m 2 /g).
- the data in Table 2 also demonstrates that the inorganic phosphate composition disclosed herein is far superior to the epoxy coatings.
- the inorganic phosphate composition has an adhesion resistance two to three times that of commercial epoxy coating, wear test results are about one fourth that of epoxy, and wear index, which represents wear loss, is about one third that of epoxy coating.
- the inorganic phosphate compositions disclosed herein are far superior to some commercial coatings available in the market.
- FIG. 1 shows the X-ray diffraction patterns of two identical samples prepared as described in Example 1, one sprayed as a thin coat and the other sprayed as a thick coat (marked as “A”). Both coatings exhibit exactly the same pattern, indicates that the coating formulation as in Example 1 may be used either as thin or thick coating.
- the main peaks of FIG. 1 represent CaSiO 3 , Mg(OH) 2 and MgKPO 4 .6H 2 O. Each peak, however, is broadened. Breadth of an x-ray diffraction peak is indicative of amorphous or microcrystalline phases.
- the X-ray diffraction pattern of Ceramicrete a chemically similar phosphate cement produced by calcined magnesium oxide, is reproduced in FIG.
- Example 2 overlaid with that of a sample Example 1.
- the data shows the corresponding peaks of the sample from Example 1 are broader than in Ceramicrete, which indicates that the amorphous content (reduced crystallinity) inorganic phosphate composition disclosed herein is substantially higher than in Ceramicrete.
- the data in FIG. 2 also shows that in the Ceramicrete, the calcined magnesium oxide peak is substantially larger than that of the inorganic phosphate composition disclosed herein, which indicates that a significant amount of magnesium oxide remains unreacted or in macrocrystalline form in the Ceramicrete.
- the reaction of oxide in the inorganic phosphate composition as disclosed herein is likely more complete and/or the amount of crystalline oxide is substantially reduced, resulting in a substantially reduced crystallinity product suitable for coatings.
- Potassium permanganate as an exemplary oxidizer, was added as an optional reagent to reduces hydrogen formation in Example 2.
- Use of an oxidizer provides improved adhesion to surfaces, such as steel/iron surfaces. Results of coatings of the composition of Example 2 on steel/substrates provided improved adhesion between the inorganic phosphate composition and the metal compared to its adhesion in the absence of the oxidizer.
- Other suitable oxidizers may be used, for example, water soluble oxidizers, such as potassium chromate, sodium chromate, or nitrates of potassium, magnesium, and aluminum.
- the X-ray diffraction pattern in FIG. 3 shows that aluminum hydroxide, which is fairly crystalline, when mixed with phosphoric acid solution in the process described above, provides a less crystalline form of the aluminum hydroxide as evidenced by the broad halo pattern.
- conventional phosphate cements such an amorphous, non-crystalline phase is insignificant or non-existent (not shown).
- the amorphous component A results in clear honey-like paste. This may be seen in photographs given in FIG. 4 . These were produced with different concentration of aluminum hydrophosphates, but all produce transparent thick gels.
- the basic component was produced by mixing wollastonite and MgO in the weight ratio of 3:1 in sufficient water to produce precursor with approximate viscosity of 10,000 centipoise. Similarly, in another experiment, mullite was added instead of wollastonite.
- the basic component was labeled B.
- the basic component may be magnesium brine having an effective amount of magnesium hydroxide.
- FIG. 5 shows the X-ray diffraction pattern of the coating along with that of wollastonite and the first acidic phosphate component for comparison.
- FIG. 6 shows the X-ray diffraction pattern of the coating produced with mullite and Part A, and also a mixture of mullite and magnesium oxide as Part B and aluminum hydro phosphate. All samples were very hard and bonded well to various substrates. The resultant coatings could not easily be scratched and could not be dislodged, even when the substrate was hit against a hard object.
- FIG. 7 shows these final coatings as sprayed in plastic cups. They all are homogeneous in appearance, smooth on the surface, and dense. Regular Ceramicrete does not exhibit these unique properties, at least because it lacks the reduced crystalline morphology that this present embodiment of the inorganic phosphate compositions disclosed herein have.
- alkaline component comprising 55 wt. % brine, 22 wt. % Class F fly ash, 6 wt. % zirconium hydroxide, 14 wt. % water, and 3 wt. % commercial paint conditioner. All components were mixed thoroughly to a form paste of approximate viscosity 10,000 centipoise.
- the acidic component was prepared as a paste by mixing 68% mono potassium phosphate and 31 wt. % water, a small amount of a suspension agent and cupric oxide to prevent formation of algae.
- the two component solutions were used in a plural spray gun at a volume ratio of acidic to alkaline components of 1:1.5. They were sprayed on mild steel plates and standard plates used for abrasion tests. After curing the plates with coatings were tested for abrasion resistance and adhesion in accordance with ASTM protocol. The average values of the results on three different samples as well as a commercial epoxy coating control are given below in Table 3.
- Example 4 the same composition as in Example 4 was prepared with the exception that instead of fly ash, mullite (3Al 2 O 3 .2SiO 2 ) in fine powder form was used instead.
- the proportion of the two components was the same as Example 4 and samples were prepared by spraying on mild steel and abrasion plates. The results of these tests are given in Table 4.
- Example 5 shows that in all respects, the inorganic phosphate composition coating comprising mullite also shows improved performance characteristics compared to the epoxy control coating.
- the adhesion resistance of Example 5 is approximately 20% higher, and abrasion performance is at least twice that of epoxy coat. This shows that fly ash coatings are not only viable but are far superior to commercial coatings.
- the first (acidic) component consisted of mono potassium phosphate (MKP) having a pH of about 4.2 when measured in aqueous solution. Calcium phosphate precursor can also be used.
- MKP powder about 74 micron size US 200 sieve
- the solution pH was adjusted between 3.2 and 3.5 by adding 2.5 wt. % phosphoric acid (added as 50% dilute solution).
- 0.5 wt. % cupric oxide was optionally added to prevent algae growth.
- the solution was adjusted with water to yield a viscosity of about 10,000 centipoise.
- the density of this component (component A) was about 1.9 g/cm 3 .
- the second component (alkaline) was prepared as follows: A requisite amount of magnesium brine solution (Martin Marietta), as a source of magnesium hydroxide, was weighed into a mixer. Zr(OH) 4 powder was added to the brine and stirred for 5-10 min until homogenous. Wollastonite passing 325 mesh was added slowly to this solution and mixed for 10-15 min. An additional amount of water was added to adjust the viscosity to approximately 20,000 to 25,000 centipoise. The density of this liquid component was 1.25 g/cm 3 and the average particle size of particles in this solution was determined to be about 5.6 micrometers or less. Thus, the second component consisted of about 69 wt. % magnesium brine (providing about 61 wt.
- MgOH brine can be substituted with MgO, preferably calcined MgO.
- MKP solids loading phosphate precursor components suitable for spray coating that can be atomized to provide thin film, paint-like coatings.
- Part A solids of Part A (e.g., MKP) and Part B (e.g. MgO). Substitutions of either Part as described above is envisaged.
- Table 5 summarizes exemplary atomizable compositions (Sample 1 & 2).
- Sample 3 To an amount of water, to which is added a required amount of 85% phosphoric acid, is added the acid phosphate precursor (e.g. monopotassium phosphate (MKP)) and mixed for less then a minute, followed by the addition of the suspension agent (e.g., xanthan gum) with mixing for 10 minutes with a high shear dispersion blade.
- MKP monopotassium phosphate
- the suspension agent e.g., xanthan gum
- a multi-channel pump, a plural piston pump, a ram discharge extruder, a two-component caulking gun or a progressive cavity pump with static mixing and air-assist for atomizing can be used.
- the two cartridges of the spray system were filled separately with the two components.
- the spray gun consisted of a mixing tube, in which the two components could be mixed prior to spraying.
- the composition was sprayed on different substrates e.g., steel, wood, hardboard, aluminum, concrete, mild steel Taber panels.
- the thickness coated was approximately 5 mil and had a noticeable color from the aggregate colorant. Coatings up to about 20 mil are achievable using the method disclosed herein.
- the coatings were allowed to cure at ambient conditions and resulted in excellent coatings with phosphate cement characteristics.
- the instant phosphate ceramic spray composition sets rapidly and at least mechanically holds the aggregate in place sufficiently to be sprayed on vertical surfaces and overhead surfaces without the aggregate migrating or falling out.
- the instant phosphate ceramic spray composition with resin coated silica aggregate does not substantially bind to the resin coating of the aggregate, thus improving the aesthetics of the coating, e.g., by not coating or covering portions of the resin coating, thus allowing the color of the aggregate to be visualized to a greater extent.
- This is augmented by the naturally semi-translucent appearance of a pigment-free phosphate ceramic resulting in a more vibrant color appearance.
- the instant phosphate ceramic spray coating can comprise other aggregate to add texture.
- the instant phosphate ceramic spray coating can comprise non-colored natural aggregate (e.g., sand, talc, etc.) to give natural finish, for example, a sand plaster type finish in a single color.
- the instant phosphate ceramic spray composition is used as a primer layer for a substrate, for example, a metal surface, and is subsequently coated with a polymer coating such as an acrylic or urethane coating.
- a substrate for example, a metal surface
- a polymer coating such as an acrylic or urethane coating.
- the metal surface can be a transportation vehicle for example, a chassis.
- aluminum oxide can be added to either or both of the first and second components in an amount sufficient to increase the hardness of the resultant phosphate ceramic.
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Abstract
Disclosed and described are multi-component inorganic phosphate formulations of acidic phosphate components and basic oxide/hydroxide components. Also disclosed are high solids, atomizable compositions of same, suitable for spray coating.
Description
- This disclosure relates to multi-component inorganic phosphate formulations of acidic phosphate components and basic oxide/hydroxide components.
- Organic synthetic materials made of epoxy, polyester, polypropylene and other polymers are widely used in composites such as fiber boards, glass fiber composites, sealants for marble and granite countertop surfaces, aircrafts, body armors etc. These resins are relatively expensive, have a high green house gas intensity and are flammable. The volatile organic compounds released by them during their use present a health hazard for a user.
- Technologies exist for formulating inorganic mineral based resins but these are usually based on alkali metal aluminosilicates and alkali metal boroaluminosilicates. These technologies for the most part are limited to one type of formulation and do not always allow for the manufacture of resins with wide range of formulations, properties and uses.
- Phosphate ceramics and ceramics that are made by acid-base reactions between phosphoric acid, or an acid-phosphate, and a metal oxide are generally known. The products disclosed in these patents are hard, and replicate properties of either cement or ceramic, or both.
- Rapidly setting compositions such as phosphate ceramics heretofore have proven difficult to spray coat (and atomize) onto surfaces so as to provide a smooth, paint-like finish. For example, conventional hydraulic cements can be sputtered coated, but the sputtered coating cannot provide a smooth, paint-like finish as it difficult to obtain good mixing with a high viscosity, unsuspended matrix, and such coatings contain significant amounts of unreacted precursor materials that tend to result in a grainy surface texture. Also, mixing a conventional hydraulic cement for extended times in order to improve its homogeneity typically results in the mixture setting before or during spray coating. Using additional aggregates with the starting precursors in these conventional formulations exacerbates the problem of providing a smooth paint-like finish, especially if such aggregates are of a size greater than about 300 mesh. Thus, conventional hydraulic cements, have heretofore not been successfully formulated such that they are reliably atomizable.
- Another problem, specific to phosphate ceramics, is that they are generally translucent after application and set. Using color aggregate in atomizible phosphate ceramics to provide color to these formulations poses challenges. Using too small a natural mineral aggregate (e.g., to avoid unwanted texture) in these formulations results in coatings that generally appear white or weakly colored and are therefore not acceptable even at greater than conventional loadings of the colorant. Using high loadings of solids and/or larger aggregates in these formulations are generally avoided for rheological difficulties and difficulty atomizing.
- On the other hand, textured, atomizable phosphate ceramic coatings, using larger aggregates (including large aggregate colorants such as colored sand aggregates) have heretofore proven difficult to achieve, partly because the larger aggregates can clog the spray/atomizing equipment and the composition must be formulated such that it can hold the large aggregate particles, but at the same time set before the aggregate migrates, for example, down a vertical surface or overhead surface. Conventional, non-ceramic paints, in contrast, provide too thin a coating to hold large aggregate for texturing and highlighting, at least in part because they have too low a viscosity and because they take too long to set.
- In general, disclosed herein are multi-component formulations comprising at least one acidic phosphate first component and at least one alkaline second component, the first and second components being suitable for providing, upon combination, an inorganic phosphate composition.
- Also disclosed herein are techniques for carrying out the chemical reactions necessary to inexpensively manufacture commercial viable inorganic synthetic compositions having high strength and other useful properties that are useful in making products and/or improving existing products. One aspect disclosed herein relates to a method for manufacturing chemically stable multi-component inorganic phosphate precursors capable of extended storage and transport. In one specific aspect disclosed herein, a method for modifying inorganic phosphate precursor solutions so as to produce high-strength, rapid-setting phosphate compositions is disclosed. In another specific aspect disclosed herein, inorganic phosphate compositions of low density, reduced crystalline morphology are provided. Other embodiments relate to a method for the manufacture of inorganic phosphate compositions for the thermal conversion to materials comprising a berlinite (AlPO4) phase, useful as a fire-resistant coating. In general, the aspects disclosed herein include manufacturing methods that use environmentally friendly techniques to provide improved efficiencies in the commercial production of these inorganic phosphate precursors and composition.
- It is also disclosed herein a solution to the aforementioned problem associated with the texturing and/or coloring of translucent phosphate ceramics formulated for spray coating and/or atomizing said compositions. Thus, the instant sprayable inorganic phosphate precursor composition comprises aggregate of up to about 30 mesh or larger and can be sprayed at a relatively thin thickness yet still hold the aggregate as well as set fast enough before the aggregate migrates or dislodges from the point of application, e.g., down a wall or from a ceiling surface. Such spray coated phosphate ceramic compositions produce high-strength, rapid-setting phosphate ceramic coatings of aesthetically pleasing colors. Such compositions can also provide corrosion protection and/or be used as an undercoating in combination with a polymeric coating, such as an acrylic- or urethane-based coating. In one aspect, said phosphate spray coating compositions are suitable for spray coating on metal surfaces, for example, structural elements and chassis of transportation vehicles such as automobiles, trains, cycles, aerospace vehicles, trucks, and buses.
- Some of the precursor components and compositions disclosed and described herein are based on phosphoric acid or phosphate salt solutions. Certain embodiments employ sparsely-soluble oxides and sparsely-soluble oxide minerals, which are oxides and oxide minerals that have limited solubility in water at neutral pH. The precursor components comprise at least one acidic phosphate component (first component) and at least one basic oxide/hydroxide component (the second component).
- In one aspect, the first component is prepared as an aqueous solution of phosphoric acid or phosphate salts such that the solution has a pH of about 1.5 to about 5. In one aspect, aqueous solutions comprising the first component having pH below 1.5 and/or above 5 are excluded.
- In another aspect, the second component is prepared by the slow addition of the sparsely-soluble oxides, or the sparsely-soluble oxide minerals to an aqueous solution of pH of 9-14.
- In yet another aspect, the sparsely-soluble oxide, or sparsely-soluble hydroxide are provided as a component of a brine solution derived from a natural source and optionally modified so as to provide an effective amount of the sparsely-soluble oxide in the form of its hydroxide. For example, magnesium brine comprising an effective amount of magnesium hydroxide, optionally with effective amounts of chlorides, oxychloride, sulphates, and oxysulphates is used. The use of such liquid sources of the sparsely-soluble oxide in the form of its hydroxide allows for the elimination or reduction of problems associated with the good wetting of individual grains of powders typically employed in the preparation of inorganic phosphate materials, and avoids or reduces any excessively exothermic reactions.
- As shown in the examples set forth below, the resulting inorganic phosphate compositions prepared from the aforementioned first and second precursor components has a unique morphological structure. The instantly mixed formulation or the set product can be used as a thin/thick coating, paint, instant adhesive, or as a matrix for composites, or as anti-corrosion or fire resistant coating for use on metal and non-metal structural materials.
- In one embodiment, a method of producing a phosphate composition is provided. The method comprises providing a first component comprising an aqueous solution of an acid-phosphate of chemical formula Am(H2PO4)m.nH2O, where A is hydrogen ion, ammonium cation, metal cation, or mixtures thereof; where m=1-3, and n=0-6; the first component solution adjusted to a pH of about 2 to about 5. A second component is provided comprising an aqueous solution of an alkaline oxide or alkaline hydroxide represented by B2mOm, B(OH)2m, or mixtures thereof, where B is an element of valency 2m (m=1, 1.5, or 2) the second component solution adjusted to a pH of between 9-14. The first component and the second component are combined together to provide an inorganic phosphate composition. Optionally, aggregate colorants can be added of a size and of an amount so as to impart a visible color to the set product.
- In a first aspect of the first embodiment, the pH of the first component is adjusted to between about 2.5 to about 5, or between about 3 to about 4.5.
- In a second aspect of the first embodiment, the first component comprises phosphoric acid, a dihydrogen phosphate salt of formula Mm(H2PO4)m and its hydrates, or mixtures thereof; where M sodium, potassium, magnesium, calcium, aluminum, or mixtures thereof, and m is 1-3.
- In a third aspect of the first embodiment, the first component comprises at least two of an alkali dihydrogen phosphate M(H2PO4) or its hydrate, phosphoric acid, an alkali earth dihydrogen phosphate M(H2PO4)2 or its hydrate, or a trivalent metal trihydrogen phosphate MH3(PO4)2 or its hydrate.
- In a forth aspect of the first embodiment, the first component comprises a metal hydrophosphate represented by the formula M3(PO4)2 and its hydrates, where M is aluminum (III), iron (III), manganese (III), lanthanides selected from lanthanum (III), cerium (III), yttrium (III), scandium (III), and mixtures thereof.
- In a fifth aspect of the first embodiment, the first component comprises mono potassium phosphate or its hydrate, in combination with one or more of phosphoric acid or aluminum trihydrogen phosphate or its hydrate such that the pH of the solution is between 2-5. A is sodium, potassium, cesium, iron (II), iron (III), magnesium (II), zinc (II), aluminum (III), bismuth (III), zirconium (IV) or mixtures thereof.
- In a sixth aspect of the first embodiment, the first component comprises phosphoric acid, alkali metal dihydrogen phosphate MH2PO4, alkali earth dihydrogen phosphate M(H2PO4)2 or its hydrate, transition metal trihydrogen phosphate MH3(PO4)2 or its hydrate, or mixtures thereof, in combination with an alkali metal oxide, alkali metal hydroxide, alkali earth metal oxide, or a basic mineral.
- In combination with any of the previous aspects of the first embodiment, the pH of the second component is adjusted to between about 9 to about 13 or between about 10 to about 12, or between about 10 to about 11.
- In combination with any of the previous of the first embodiment, the second component comprises an oxide represented by the formula BO, or a hydroxide represented by the formula B(OH), where B is an alkali earth metal or transition metal. B may be sodium, potassium, magnesium, calcium, zinc, barium, aluminum, yttrium, a lanthanide, zirconium, iron, bismuth or manganese. The second component may be an oxide or hydroxide of: magnesium, barium calcium, zinc, iron(II), manganese (II), or mixtures thereof.
- In combination with any of the previous of the first embodiment, the second component is magnesium brine having a pH of about 9 to about 11, or about 10 to 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide. The magnesium hydroxide may be characterized by having a hexagonal platelet morphology. The magnesium brine may further contain an effective amount of magnesium hydroxide, magnesium chloride, magnesium sulphate, magnesium oxychloride precursor, magnesium oxysulphate precursor, or mixtures thereof.
- In combination with any of the previous aspects of the first embodiment, the second component comprises particulate matter having an average minimum surface area of greater than 5 m2/g. In combination with any of the previous aspects of the first embodiment, the second component further comprises wollastonite, talc, fly ash, kaolin clay, kaolinite, meta kaolin, mullite, calcium aluminate minerals, calcium silicate minerals, aluminum silicate minerals, calcium aluminum silicate minerals, or mixtures thereof, in a weight ratio of between 1:0.05 to 1:6 of the second component.
- In a seventh aspect of the first embodiment, the first component is mono potassium phosphate or its hydrate, and the second component is magnesium brine having a pH of about 9 to about 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide.
- In an eighth aspect of the first embodiment, the first component is mono potassium phosphate or its hydrate, and the second component is magnesium brine having a pH of about 9 to about 11, wherein the magnesium brine contains an effective amount of magnesium hydroxide, magnesium chloride, magnesium sulphate, magnesium oxychloride phosphate precursor, magnesium oxysulphate phosphate precursor, or mixtures thereof.
- In a ninth aspect of the first embodiment, the first component comprises Mg(H2PO4)2 or its hydrate, and the second component comprises an alkali metal oxide or alkali metal hydroxide.
- In a tenth aspect of the first embodiment, the first component comprises AlH3(PO4)2 or its hydrate, and the second component comprises an alkali metal oxide or alkali metal hydroxide.
- In combination with any of the previous aspects of the first embodiment, the resultant reaction product is of reduced crystalline morphology or reduced nucleation centers. In combination with any of the previous aspects of the first embodiment, the first component or the second component has an average particle size of less than 50 micron.
- In an eleventh aspect of the first embodiment, the second component is alkali earth metal oxy-chloride phosphate precursors, alkali earth metal oxy-sulfate phosphate precursors, or mixtures thereof.
- In combination with any of the previous aspects of the first embodiment, the second component further comprises fillers wollastonite (CaSiO3), talc (Mg3Si4O10(OH)2, mullite (alumino silicate), both Class C fly ash and Class F fly ash, the reactive filler present in a weight ratio of 1:0.5 to 1:6 to the second component. In combination with any of the previous aspects of the first embodiment, a product prepared by the process as defined in the first embodiment is provided.
- In a second embodiment, an inorganic phosphate compound is provided. The compound is of the general formula: B(A3-mPO4)s; wherein A has a valency of m=1 or 2; and B has a valency of s=1, or 2; B(A(2/m)PO4)s; wherein A has a valency of m=1 or 2; B has a valency of s=1, or 2; (2/m)A3Bm(PO4)2; wherein A has a valency of m=1 or 2; B has a valency of 3; or B(AOPO4)s; wherein A has a valency of 4 and s=1 or 2; and B has a valency of 1, or 2; wherein the inorganic phosphate i-iv has at least one of the following characteristics: a substantially reduced amount of calcined alkali/alkali earth oxide particles present as measured b x-ray diffraction; or a reduced crystalline morphology as measured by x-ray diffraction relative to a compositionally similarly inorganic phosphate ceramic or; a reduced density, relative to a compositionally similarly inorganic phosphate ceramic.
- In a first aspect of the second embodiment, the density of the inorganic phosphate is less than 1.8 g/cm3 or less than 1.5 g/cm3. In combination with any of the previous aspects of the second embodiment, the compound is Na2KPO4. NaK2PO4. MgKPO4. Mg(ZnPO4)2. Mg(K2PO4)2. Mg2KPO4. Mg(ZnPO4)2. Mg(K2PO4)2. AlK3(PO4)2. Al2Mg3(PO4)2. ZrOKPO4. Mg(ZrOPO4)2. Zr(OH)2KPO4. or Mg[Zr(OH)2PO4)2]2.
- In a third embodiment, a method of producing an oxy phosphate-containing composition is provided, the method comprises: providing a first component comprising a solution of an oxy-phosphate of chemical formula (MO)(H2PO4)2 and its hydrates, where M is an element of valency 4 and m=1-3, wherein the first component solution is adjusted to a pH between 2-5; providing a second component comprising a solution of an alkaline oxide or alkaline hydroxide represented by B2mOm or B(OH)2m where B is an element of valency 2m (m=1, 1.5, or 2); and combining the first component and the second component together.
- In a first aspect of the third embodiment, M is zirconium (IV). In a second aspect of the third embodiment, the pH is adjusted to between 2-5 or the pH is adjusted to between 3-4.5, or the pH is adjusted to between 3-3.5. In combination with any of the previous aspects of the third embodiment, the first component comprises magnesium oxychloride, magnesium oxysulfate, or mixtures thereof, in combination with an amount of hydrochloric acid or sulfuric acid to reduce the pH to between 2 to 5. In combination with any of the previous aspects of the third embodiment, a product prepared by the process as defined in the third embodiment is provided. In combination with any of the previous aspects of the third embodiment, the second component comprises zirconium compounds, zinc compounds, or mixtures present in an amount of between 0-5 wt. % of the second component.
- In a forth embodiment, a method of producing berlinite is provided. The method comprises: providing a first component comprising aluminum trihydrogen phosphate AlH3(PO4)2. or its hydrates; providing a second component comprising aluminum hydroxide; combining the first component and the second component together; and heating the combination at an elevated temperature sufficient to form a berlinite phase (AlPO4) detectable by x-ray diffraction.
- In a fifth embodiment, a method of producing a high-temperature resistant coating is provided. The method comprises: providing a first component comprising aluminum trihydrogen phosphate AlH3(PO4)2. or its hydrates; providing a second component comprising aluminum hydroxide; combining the first component and the second component together; and contacting a surface of an article with the combination of the first component and the second component; heating the surface of the article at an elevated temperature sufficient to form a coating comprising a berlinite phase (AlPO4) detectable by x-ray diffraction.
- In a sixth embodiment, a method of producing aluminum trihydrogen phosphate (AlH3(PO4)2. or its hydrates is provided. The method comprises heating a solution comprising at least one of aluminum oxide or aluminum hydroxide or aluminum oxide hydrate, and phosphoric acid to an elevated temperature for a time sufficient to dissolve to a maximum amount the at least one of aluminum oxide or aluminum hydroxide or aluminum oxide hydrate; and cooling to form a viscous solution.
- In a first aspect of the sixth embodiment, the method further comprises adding about 0.5 wt. % to about 2 wt. % of a source of fluoride ion to the solution. In combination with the previous aspect of the sixth embodiment, the method further comprising adding about 0.2 wt. % to about 1 wt. % of an oxidizer to the solution. In combination with any of the previous aspects of the sixth embodiment, the oxidizer is selected from potassium permanganate, potassium chromate, sodium chromate, a soluble nitrate of potassium, magnesium, or aluminum. In combination with any of the previous aspects of the sixth embodiment, the method further comprises combining with the viscous solution at least one of magnesium brine, magnesium hydroxide or magnesium oxide to form a reactive mixture; and applying the reactive mixture on a substrate.
- In a seventh embodiment, an atomizable phosphate ceramic composition is provided. The atomizable phosphate ceramic composition comprising a first component comprising an aqueous solution of an acid-phosphate of chemical formula Am(H2PO4)m.nH2O, where A is hydrogen ion, ammonium cation, metal cation, or mixtures thereof; where m=1-3, and n=0-6; the first component solution adjusted to a pH of about 2 to about 5; a second component comprising an aqueous solution of an alkaline oxide or alkaline hydroxide represented by B2mOm, B(OH)2m, or mixtures thereof, where B is an element of valency 2m (m=1, 1.5, or 2) the second component solution adjusted to a pH of between 9-14; and a rheology modifier/suspending agent in an amount capable of providing shear thinning of either the first component or the second component and further capable of suspending a high solids content of either the first component or the second component for atomization. Optionally, aggregate material is present in an amount in at least one of the first and the second component capable of imparting an observable color and/or texture. The first component can comprise mono potassium phosphate or its hydrate, in combination with one or more of phosphoric acid or aluminum trihydrogen phosphate or its hydrate such that the pH of the solution is between 2-5. The first component can comprise mono calcium phosphate or its hydrate. The first component, A can be sodium, potassium, cesium, iron (II), iron (III), magnesium (II), zinc (II), aluminum (III), bismuth (III), zirconium (IV) or mixtures thereof. The first component preferably comprises phosphoric acid, alkali metal dihydrogen phosphate MH2PO4, alkali earth dihydrogen phosphate M(H2PO4)2 or its hydrate, transition metal trihydrogen phosphate MH3(PO4)2 or its hydrate, or mixtures thereof. The second component can be an oxide represented by the formula BO, or a hydroxide represented by the formula B(OH)2, where B is an alkali earth metal or transition metal, wherein B is sodium, potassium, magnesium, calcium, zinc, barium, aluminum, yttrium, a lanthanide, zirconium, iron, bismuth or manganese. The second component can be an oxide or hydroxide of magnesium, barium calcium, zinc, iron(II), manganese(II), or mixtures thereof. The second component can be magnesium brine having a pH of about 9 to about 11. The phosphate ceramic spray composition can further comprise aluminum oxide present in an amount sufficient to increase the hardness of the phosphate ceramic. Solids content of up to about 75 wt % for either the first or second component can be used.
- In combination with any of the previous aspects of the seventh embodiment, the rheology modifer/suspending agent is at least one of guar gum, diutan gum, welan gum, and xanthan gum. In combination with any of the previous aspects of the seventh embodiment, the aggregate is present in an amount of at least about 1 wt % to about 60 wt %. In combination with any of the previous aspects of the seventh embodiment, the aggregate is at least one of a resin coated silica and a naturally colored mineral aggregate. The aggregate can be of an average particle size of about 20 mesh micron to about 400 mesh. In combination with any of the previous aspects of the seventh embodiment, the aggregate is of an average particle size of at least about 20 mesh or less and, after application of a coating of less than about 20 mil, the sprayed phosphate ceramic coating substantially retains the aggregate in the coating on a vertical surface or an overhead surface.
- In an eighth embodiment, a method of atomizing a phosphate ceramic, the method comprising providing (i) a first component comprising an aqueous solution of an acid-phosphate of chemical formula Am(H2PO4)m.nH2O, where A is hydrogen ion, ammonium cation, metal cation, or mixtures thereof; where m=1-3, and n=0-6; the first component solution adjusted to a pH of about 2 to about 5; and (ii) a second component comprising an aqueous solution of an alkaline oxide or alkaline hydroxide represented by B2mOm, B(OH)2m, or mixtures thereof, where B is an element of valency 2m (m=1, 1.5, or 2) the second component solution adjusted to a pH of between 9-14; wherein the second component is separated from the first component prior to atomization; (iii) a rheology modifer/suspending agent in an amount capable of providing shear thinning of either the first component or the second component prior to exiting the dispensing device and further capable of suspending a high solids content of either that results in a decrease in the viscosity of the composition the first component or the second component for atomization; and atomizing the first component and second component. The first and second components can be as described above for the seventh embodiment. Optionally, aggregate material can be present in an amount in at least one of the first and the second component capable of imparting an observable color and/or texture. In one aspect, the step of atomizing comprises urging the first component and the second component through an atomizing orifice using at least one of a multi-channel pump, a plural piston pump, peristaltic pump, a ram discharge extruder, and a progressive cavity pump.
- In combination with any of the previous aspects of the eighth embodiment, the step of atomizing further comprises a mixer configured to mix the first component, the second component, and the aggregate. In combination with any of the previous aspects of the eighth embodiment, the step of atomizing comprises dispensing the first and second components essentially simultaneously. In combination with any of the previous aspects of the eighth embodiment, the rheology modifer/suspending agent is at least one of guar gum, diutan gum, welan gum, and xanthan gum.
- In combination with any of the previous aspects of the eighth embodiment, the aggregate is present in an amount of at least about 1 wt % to about 60 wt %. The aggregate can be of an average particle size of about 20 mesh to about 400 mesh. The aggregate can be at least one of an aggregate colorant comprising a naturally colored mineral aggregate and an aggregate colorant comprising resin coated silica. In combination with any of the previous aspects of the eighth embodiment, the aggregate is of an average particle size providing surface texture to the spray composition after application. In combination with any of the previous aspects of the eighth embodiment, the method further comprises the step of forming a coating of less than about 20 mil thickness and retaining the aggregate in the coating when applied to a vertical surface or overhead surface, wherein the aggregate is at least 400 mesh.
- An understanding of the aspects disclosed and described herein, summarized above, may be had by reference to the appended drawings, some of which illustrate the results obtained from the examples set out below. Accordingly,
-
FIG. 1 . Depicts an X-ray diffraction pattern of a thin coating (blue) and thick coating of magnesium potassium phosphate composition as disclosed and described herein. -
FIG. 2 . Depicts an X-ray diffraction pattern of a conventional Ceramicrete (a phosphate cement). -
FIG. 3 . Depicts an X-ray diffraction pattern of alumophosphate (AlH3(PO4)2.2.5H2O) A, and Al(OH)3 as disclosed and described herein, evidencing a reduced crystalline or amorphous phase. -
FIG. 4 . Is a photograph of an aluminum hydrophosphate gel as disclosed and described herein. -
FIG. 5 . Depicts an X-ray diffraction pattern of a coating produced from aluminum hydro phosphate, wollastonite, and magnesium oxide as disclosed and described herein. -
FIG. 6 . Depicts an X-ray diffraction pattern of an alumophosphate, MgO and mullite sample disclosed and described herein compared with pure mullite and alumophosphate are shown for comparison. -
FIG. 7 . Depicts coatings produced by using aluminum hydro phosphate and magnesium oxide precursor materials as disclosed and described herein. - In various aspects, a multi-component formulation is provided, comprising at least one acidic component and at least one alkaline component. Both components of the multi-component formulation are provided as solutions, emulsions, dispersions, pastes, or combinations thereof. Each of the components are produced separately and stored separately, and may be dispensed separately or in combination. The components ultimately are combined prior to or during application and are allowed to react to form an inorganic phosphate composition.
- The resultant reaction products of the multi-component formulation are near neutral in pH and may provide refractory-like compositions that are stable at very high temperature, for example, exceeding 2000° F., e.g., temperatures where most of the commercial organic-based products and some inorganic produces can not survive.
- In another embodiment, the above formulations are provided as suitable coatings and/or paints and are formulated for high solids spray coating. Up until now, it has been difficult to spray a suspension of ceramic precursor solutions with high solids content and obtain a coating that is smooth or does not result in the migration of the aggregates (or the substantial retention of the aggregates in the coating) after application to a surface. Indeed, the same can be said of conventional spray coating of hydraulic cements. Using spray equipment with aggregate-containing formulations as conventional paint/coating formulations has been problematic for a number of reasons, some of which include the difficulty of passing larger-sized aggregates through small orifices of spray equipment and even more so, the difficulty of keeping such aggregates from migrating once they are sprayed on a surface. Likewise, the ability to atomize such aggregate-containing formulations and obtaining acceptable coated surfaces has been elusive. Decreasing the set time of the formulation provides only a partial solution to this problem and is generally inapplicable for conventional paints.
- Applicants have thus provided ceramic formulations that are capable of spray coating, as well as capable of atomization so as to provide a “paint-like” appearance. In fact, it is difficult to distinguish the instant set coatings from a conventional paint coatings on a surface. Like conventional paints, the instant formulations can be directly sprayed on surfaces, e.g., metal surfaces, concrete surfaces, and other structural surfaces, but in contrast, the instant formulations provide functional, value-added properties at a level not possible from conventional paints, such as metal corrosion protection and fire resistance.
- By a combination of rheology control and dispersion of the solids in the formulation components (parts A and B), paint-like final coatings of ceramics are provided using conventional spray equipment. It is further been demonstrated that aggregate colorants can be effectively incorporated into the already high-solids formulation components so as to provide colored coatings. It has also been demonstrated to provide textured surfaces of the instant formulations using aggregates of larger size, e.g., sand. Using a rheology modifer/suspending agent in an amount capable of providing shear thinning of either the first component or the second component and further capable of suspending a high solids content of either the first component or the second component for atomization, excellent paint-like coatings are obtained.
- Addition of aggregates to the high solids components of the instant disclosure is believed possible because the of the adjusted viscosity of the components, their density, and their ability to set rapidly (to provide at least a mechanical hold of the aggregate). Conventional paints and most hydraulic cements simply cannot hold aggregate of large size (either for coloring or texturing) because of at least their inability to set quickly. As a result, the instant formulations differ from these conventional coatings in that they can provide a range of coatings, for example, from a Venetian sand plaster finish, to a brightly colored satin-finish-like coating not otherwise obtainable from conventional hydraulic cements or conventional paints.
- In one aspect, a sprayable ceramic coating comprises a first component and a second component, a suspension agent, aggregates of particle size of less than about 30 mesh, and a rheology modifier.
- Acidic phosphate component: The acidic phosphate component consists of phosphoric acid and/or an acid-phosphate of formula, Am(H2PO4)m.nH2O, where A is an m-valent element such as sodium (Na, m=1), potassium (K, m=1), magnesium (Mg, m=2), calcium (Ca, m=2), aluminum (Al, m=3) etc. A may also be a reduced oxide phase when higher-valent oxides are used. For example, for iron, which exists in valence state of +2 and +3 (FeO and Fe2O3 as oxides), A can be the metal of lower oxidation state. It can also be a cation of oxides of four-valent metal oxide such as ZrO2+, in which case m=2 nH2O in the formula above is simply the bound water, where n can be any number, normally ranging from 0 to 25.
- It is possible to use hydro phosphates of trivalent metals such as aluminum, iron and manganese represented by the formula AH3(PO4)2.nH2O, where A is a transition metal that includes aluminum, iron, manganese, yttrium, scandium, and all lanthanides such as lanthanum, cerium, etc.
- In case the pH of the acidic precursor is higher than needed for instant reaction, phosphoric acid may be added and the pH may be adjusted to bring down the pH. A preferred pH selected is between 3 and 4, and the most preferred pH is between 3 and 3.5. either elevating the pH of phosphoric acid or that of an acid-phosphate such as magnesium dihydrogen phosphate (Mg(H2PO4)2) or aluminum trihydrogen phosphate (AlH3(PO4)2) by neutralizing partially using an alkaline oxide, hydroxide, or a mineral, or by acidifying a dihydrogen phosphate such as mono potassium phosphate (KH2PO4) that has a pH greater than 3.5 by adding a small but appropriate amount of phosphoric acid or a low pH acid phosphate such as Mg(H2PO4)2 or aluminum trihydrogen phosphate AlH3(PO4)2. Examples described later in this document provide the art of adjusting this pH.
- Often the acid-phosphate used in the precursor is only partially soluble. In such a case, the precursor is milled so that the average particle size passes through 230 mesh sieve (less than 70 micron).
- For oxychloride and oxysulfate compositions, the acidic component consists of magnesium oxychloride, and magnesium oxysulfates appropriately acidified with either hydrochloric acid or sulfuric acid to reduce the pH.
- Water may be added to the precursor component to reduce the viscosity thereof, or other types of viscosity reducing agents may be used. Commercial additives that prevent algae growth may also be added to this precursor so that no algae growth occurs during storage of this precursor.
- Basic precursor: The basic precursor generally consists of a sparsely soluble oxide, or preferably a hydroxide with an average particle size less than 70 micron. The oxide may be represented by the formula B2mOm or B(OH)2m, where B is a 2m-valent metal. All divalent metal oxides (m=1), and some trivalent metal oxides in reduced state fall into this category of sparsely soluble oxides. Examples of divalent oxides are, but not limited to, magnesium, barium, zinc, calcium. Examples of trivalent oxides in reduced state are iron oxide (FeO), and manganese oxide (MnO).
- For paints, coatings, adhesives and seals, it is desirable to obtain at least some amorphous or glassy phase in the coating, so that this phase will fill the surface irregularities of the substrate and form into an impermeable, dense, and smooth coating. It has been discovered that it is possible to develop such structure by using magnesium hydroxide (Mg(OH)2) instead of calcined MgO. Mg(OH)2 reacts with an acid-phosphate instantly resulting in two favorable consequences. First, the crystalline growth cannot occur due to very short time of reaction. Secondly, since the solubility of Mg(OH)2 is much higher than that of calcined MgO, most of it dissolves and hence there will not be many nucleation centers for any crystalline growth of the reaction product. The net result is a greater amorphous structure.
- By using uncalcined oxide powders it was previously difficult to carry out the methods of producing acid-base ceramics suitable for spray coating in conventional spray equipment and for providing colored or smooth finishes. Ceramics typically need crystalline structure for three dimensional stability and rigidity. In contrast, non-ceramic coatings typically attach to a substrate and get two dimensional rigidity from the substrate. For at least this reason, use of uncalcined oxides or hydroxides are herein disclosed and described as basic precursors produce substantially reduced crystalline inorganic phosphate compositions useful as coatings and also useful for sprayable coatings. In one aspect, the use of uncalcined oxides or hydroxides as basic precursors to produce substantially reduced crystalline inorganic phosphate compositions as herein disclosed and described provides a major distinction and a substantial improvement over conventional phosphate ceramics. On the other hand, the use of calcined oxides can provide for improved coloring of the set coating over the uncalcined oxides or hydroxides.
- Calcining oxides is a major source of energy consumption in acid-base cements and coatings. This can be eliminated by using uncalcined oxides and hydroxides. For example, in one aspect a brine of Mg(OH)2 obtained directly from magnesia mines provides for a suitable source of the first component alone or in combination with other basic minerals or filler. The brine contains at least about 60% dissolved, suspended or dispersed Mg(OH)2 and can be used directly to provide the second alkaline component of the inorganic phosphate composition.
- In at least one aspect, a two part component system is provide, one part is an acidic phosphate precursor component whose pH lies between 2-5, 2.5-4.5 in a preferred range, and 3-4.5 range in the most preferred range. A basic precursor component having a pH range from 9-14, a preferred range of 10.5-12, and 11-12 in the most preferred range.
- When divalent metal oxide is used, the acid-base reaction that forms the inorganic phosphate composition is given by equation (1):
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Am(H2PO4)m .nH2O+B(OH)2m +sH2O=A(BPO4)m+(n+m+s)H2O. (1) - The first compound on the right hand side of Eq. (1) is the acid phosphate precursor material, which may be a hydrate. The second compound is the base precursor material, which may also be a hydrate. For example, mono potassium phosphate (KH2PO4) as the acid phosphate and magnesium hydroxide as the alkaline material, provides A=K, m=1, and B=Mg, and n=0, which results in the following equation for the acid base equation (2).
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KH2PO4+Mg(OH)2+4H2O=MgKPO4.6H2O (2) - While similar reactions have been used in producing ceramics of MgKPO4.6H2O, (see for example, Chemically Bonded Phosphate Ceramics, by Arun Wagh, Elsevier pub., 2004), such cements were made using calcined magnesium oxide, in contrast to a liquid, paste, dispersion or emulsion source of magnesium hydroxide. Thus, while the same chemical formula is theoretically prepared, the inorganic phosphate disclosed and described herein is substantially more amorphous (reduced crystallinity) than previously prepared MgKPO4.6H2O.
- Moreover, in at least one aspect, it has been discovered that when the acidic phosphate precursor component has an element with a valency of m, where m is greater than 1, for example, Mg(H2PO4)2 (m=2), oxides or hydroxides of an alkali metal, such as that of Na or K in the base precursor material may be used as a paste, dispersion or emulsion. The acid-base reaction that produces the inorganic phosphate composition for the example discussed above is given by equation (3):
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Am(H2PO4)m .nH2O+2mB(OH)=AB2m(PO4)m+(n+m)H2O (3) - The resultant water fraction evaporates providing the inorganic phosphate composition. Mg(OH)2 may be used as a very fine powder passing—less than 70 micron (mesh 230-235). It may be reacted with an acid-phosphate that exhibits a pH greater than 3. For example, one may use mono potassium phosphate solution, whose pH is 4.2, and bring down its pH by adding small amount of phosphoric acid or a di hydrogen phosphate of very low pH, such as aluminum di-hydrogen phosphate (AH3(PO4)2.nH2O)., whose pH is approximately 1.2. Use of Mg(OH)2 reduces the energy consumption in the life cycle cost of the product and hence also reduces green house gas release in the entire process. As discussed above, it is possible to raise the pH of alkaline component to dissolve more hydroxide to very high pH, and if needed, one can go to the maximum pH of 14. However, handling of such very alkaline products is difficult, and therefore a maximum pH of 11 is recommended. As discussed below, magnesium brine, which has a pH of about 10.2, works very well.
- Once the acid and alkaline solutions are optimized for their solubility, pH, and optionally viscosity, the inorganic phosphate composition is formed by combining the first and second precursor components. Suitability and proportion of these components and their compatibility is governed by the stoichiometry of the acid-base reaction. Table 1 summarizes these combinations, and the chemical formulae for the resulting inorganic phosphate compositions.
- In Table 1, the water, which is either added to initiate the reaction, or is the water formed during reaction, may be present as free or bound water. Table 1 does not distinguish between the two, but that distinction is of little consequence because the free water will evaporate when the product is dried, but the bound water will remain in the structure. Amount of the bound water may be estimated by using conventional analytical tools and techniques, such as differential scanning calorimetry, for example.
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TABLE 1 Summary of acid-base reactions that can occur in forming the inorganic phosphate composition products Components General equations Examples Monovalent sAm (3-m)O + Bs(H2PO4)s = m = 1, s = 1 and divalent B(A3-mPO4)s + sH2O Na2O + KH2PO4 → metal oxides, A has a valency of Na2KPO4 + H2O and monovalent m = 1 or 2. m = 2, s = 1 and divalent B has a valency of MgO + KH2PO4 → metal s = 1, or 2. MgKPO4 + H2O phosphates m = 2, s = 2 2ZnO + Mg(H2PO4)2 = Mg(ZnPO4)2 + 2H2O m = 1, s = 2 2K2O + Mg(H2PO4)2 → Mg(K2PO4)2 + 2H2O Monovalent (2s/m)Am(OH )m + m = 1, s = 1 and divalent Bs(H2PO4)s = 2NaOH + KH2PO4 → metal B(A(2/m)PO4)s + 2sH2O Na2KPO4 + 2H2O hydroxides, and A has a valency of m = 2, s = 1 monovalent and m = 1 or 2. Mg(OH)2 + KH2PO4 → divalent metal B has a valency of MgKPO4 + 2H2O phosphates s = 1, or 2. m = 2, s = 2 2Zn(OH)2 + Mg(H2PO4)2 → Mg(ZnPO4)2 + 4H2O m = 1, s = 2 2KOH + Mg(H2PO4)2 → Mg(K2PO4)2 + 4H2O Monovalent 3Am (2/m)O + 2B3H3(PO4)2 = m = 1 and divalent (2/m) A3 Bm(PO4)2 + 3K2O + 2AlH3(PO4)s → metal oxides, 3H2O 2AlK3(PO4)2 + 3H2O and trivalent A has a valency of m = 1 m = 2 metal or 2; B has a valency of 3; 3MgO + AlH3(PO4)s → phosphates Al2Mg3(PO4)2 + 3H2O Quadrivalent Quadrivalent oxides S = 1 metal oxides or sAO2 + Bs(H2PO4)s = ZrO2 + KH2PO4 → hydroxides, and B(AOPO4)s + sH2O ZrOKPO4 + H2O divalent metal A has a valency of 4; B S = 2 phosphates has a valency of 1 or 2; 2ZrO2 + Mg(H2PO4)2 → and s = 1 or 2. Mg(ZrOPO4)2 + 2H2O Quadrivalent oxides S = 1 sA(OH)4 + B(H2PO4)s = Zr(OH)4 + KH2PO4 → B[AOH)2PO4)s + 2sH2O Zr(OH)2KPO4 + 2H2O A has a valency of 4; B S= 2 has a valency of 1 or 2; 2Zr(OH)4 + Mg(H2PO4)2 → and s = 1 or 2. Mg[Zr(OH)2PO4)2]2 + 4H2O - In Table 1, examples of monovalent elements are sodium (Na), potassium (K), or ammonium (NH4). Similarly, major divalent elements one may use are magnesium, calcium, zinc, barium etc., while trivalent elements are aluminum, iron etc., and an example of quadrivalent element is zirconium (Zr). Other elements may be used that fit into the combinations given above and the disclosure and claims are should not to be limited by the examples given above.
- Though the stoichiometry dictates the composition of the adhesive, it is not possible to exactly tailor that composition in a production process. Typically, the basic oxide and hydroxide precursor content is kept at a stoichiometric higher amount compared to the acid-phosphate precursor content. This provides a product that is substantially free of any residual acid.
- Cements and ceramics may generally be produced by using acidic phosphate and oxides and oxide minerals. These cements and ceramics are typically formed by mixing an acid-phosphate and the solid oxide in water. This mixture is used immediately and ultimately sets into a solid product within hours. These formulations of precursors and the overall process, however, is not useful for producing formulations suitable for dispensing, for example, as thin film coatings and the like. At least some of the reasons for this include, for example: such compositions are rapid-setting cements containing particulate matter; and maximum working times after combining and before setting is only couple of hours. Thus, they do not have a shelf life needed for paints and coatings. To produce a smooth, thin coating, it is typically necessary to use very fine particles as components. Generally, this is not a requirement in 3-D cement forming and ceramic fields. In fact, finer particles increase the surface area of exposure to acid-base reactions. For example, it has been disclosed that the limits on the surface area may be 0.3-0.55 m2/g, which is a very small range and not generally suitable for certain applications, including for example, coatings. It has further been disclosed that the maximum allowable surface area of 0.55 m2/g is also too small for certain applications, including for example, coatings. Paints and coatings, for example, typically require much finer particles with large surface area, for example, greater than about 5 m2/g, more preferably greater than about 10 m2/g for instant reaction and smoothness of the applied coating surface.
- During setting of conventional acid-base phosphate cements, an exothermic acid-base reaction releases heat and heats the reacting mixture, which may help setting. For thin coatings, a significant amount of this exothermic heat is dissipated due to the large surface area of a relatively thin coat. In particular, in spray coating, which is the most efficient way of coating large areas, the acid-base precursor media is atomized; the atomization cools the media by several degrees which inhibits the acid-base reaction on the surface of the substrate. This leads to dripping (or rebound) of unreacted media from vertical/overhead surface such as walls/ceilings, and also gives efflorescence on the dried surface. For this reason, the compositions of paints and coatings need to be tailored to instant reaction that produces higher amount of exothermic heat that will harden the sprayed product. This is another reason, why large surface area of particles is needed for conventional cements.
- Conventional paints and coatings are generally organic polymers and they are typically non crystalline, amorphous materials upon use. On the other hand, acid-base phosphate cements or ceramics, discussed above, consist of crystalline or glass-crystalline materials with a significant crystalline phase after setting. As a result, conventional acid-base phosphate ceramics are not generally suited for coatings, paints, and adhesives, for example, in view of their significant crystal structure that otherwise provides an undesirable grainy structure. What has been discovered and disclosed herein is a substantially reduced crystalline inorganic phosphate composition suitable for thin film coatings, paints, and adhesives. It has been discovered that by changing the precursor materials to provide solutions, dispersions, emulsions, and/or pastes, substantially reduced crystalline inorganic phosphate compositions can be produced.
- In addition, even with conventional precursor starting materials and a high solids loading up to 75 wt. % solids of either precursor component, by a combination of rheology control and dispersion of the solids in the formulation components (parts A and B), paint-like final coatings of ceramics are provided using conventional spray equipment. It is further been demonstrated that aggregate colorants can be effectively incorporated into the already high-solids formulation components so as to provide colored coatings. It has also been demonstrated to provide textured surfaces of the instant formulations using aggregates of larger size, e.g., sand.
- Dispensing of the components may be done using conventional dispensing equipment, such as for example, a dual source extruder, rams, pumps etc. fitted with a suitable spray gun, optionally with an in-line static mixer. In one aspect, the spray equipment excludes texture guns as they typically are used for hydraulic cement dispensing/sputtering.
- In at least one aspect, a multi-component formulation is disclosed and described that provides at least one or more of the following properties prior to combining the respective components, or after combining: providing viscosities of the individual components less than about 35,000 centipoise in general, preferably less than about 15,000 centipoise; bonding/adhering to a substrate, the individual components when dispensed, or within a short time thereafter so that they are not adversely affected by exposure to different atmospheric conditions such as rain, sun, and wind; bonding to the substrate a hard and dense set coating that meets standards designed for a particular application such as fire protection, corrosion resistance, chemical resistance, architectural appeal, etc.; exhibit long term durability against the entire solar spectrum, and heat and cooling cycles for the set coating; providing a pH greater than about 2 for the acidic phosphate precursor component and a pH of less than about 12 for the basic precursor component to avoid occupational hazard and to protect environments during any use, disposal or spill; providing essentially homogeneous components during storage, and segregation of water not occurring during pumping and storage. If segregation does occur during storage and transport, the components can be re-mixed easily prior to application back into a homogenous state; minimizing the tendency of the basic precursor to harden by pozzalinic reaction during storage for at least six months; and/or preventing bioactivity of the acidic precursor.
- The coatings prepared as disclosed here are durable, are not deteriorated by ultra violet radiation, and certain formulations are reflective to infra red radiation and, hence, support energy conservation in a building. The disclosed compositions are suitable for primers and top coats as they provide excellent bonding to a variety of substrates.
- Because the acid-base reactions that produce paints, coatings, or adhesives are instantaneous, a suitable applicator system is needed. A plural system, in which the acid and base precursor materials can be stored separately in the proportion desired, and then can be dispensed. For example, the inorganic phosphate composition precursors can be introduced in a mixing chamber during application or mixed upon exiting a spray device. Such systems are common in the market, and can be adapted for dispensing acidic and/or alkaline components without deteriorating the inner surface or components of the device.
- The viscosity of the two components should be sufficiently low so that dispensing is facilitated. Generally, either precursor viscosity of less than 35,000 centipoise (cp) or less is acceptable for many pumps, but a viscosity of less than 15,000 cp is preferable.
- For acid component, this is not an issue as most acid-phosphates exhibit low viscosity. Mono sodium phosphate being highly soluble, it meets this requirement easily. Mono potassium phosphate has a low solubility (20 g/100 ml) and much of the phosphate remains in suspension. Therefore, its viscosity needs to be lowered. This may be done by milling the solution of mono potassium phosphate solution. Other exemplary acid-phosphates, such as magnesium dihydrogen phosphate (Mg(H2PO4)2), or aluminum tri hydrogen phosphate (AlH3(PO4)2) also have low solubility and hence may also need to be milled to produce low viscosity precursor components. Generally, addition of excess water is not desirable, because it results in too much water in the final reacting mixture and setting of one or more of the components may occur.
- For the alkaline component, the viscosity depends on the amount of powder material in the solution. The oxide powders or the mineral powders used in the solution have to be very fine in nature and are ground to pass −325 micron sieve size. Brine of Mg(OH)2 is ideal for this purpose because it exhibits a low viscosity and hence no processing of brine is needed.
- The viscosity of the second component (base precursor) may be adjusted by adding partially reactive minerals such as wollastonite (calcium silicate, CaSiO3), or mineral containing materials such as fly ash. Class F fly ash is preferred because the small amount of carbon acts as a lubricant on particles and helps reduce the viscosity of the precursor components. The content of the additive may range from an amount equal to the second precursor component to twice that. If other oxides are used, the amount may be adjusted correspondingly to obtain a viscosity less than 15,000 cp.
- In addition to the methods described above, viscosity may also be adjusted by adding commercial waterbourne paint conditioners in a small quantity, which can adjust (e.g., reduce) the viscosity as needed.
- As mentioned above, it is desirable that both the acidic and alkaline precursor components should have good shelf life, preferably greater than 6 months, greater than one year, or greater than 18 months. During this time, there should be insignificant segregation of particles and the liquid fraction, or, it should be easy to re-mix the components into a homogeneous or semi-homogenous mass suitable for dispensing at the time of application. This may be done, for example, by milling the acid component so as to produce a homogenous precursor and then optionally adding one or more commercial suspension agents, if necessary.
- Obtaining a long shelf life for alkaline component is more difficult. This is because, alkaline oxide components tend to undergo pozzalinic reactions (reaction that occurs in Portland cement or in wet fly ash), in the presence of moisture such that the alkaline powder sets by itself into a hard mass resulting in difficulty reconstituting and/or grinding the hardened mass for use.
- Generally the pozzalinic reaction is associated with calcium content in cement industry. Thus, limiting calcium content in the alkaline component can solve this problem. For example, using Class F fly ash, which has the least amount of free calcium, or limiting the amount of wollastonite, so that excess calcium is not released. Class C fly ash should generally be avoided in the alkaline composition because this ash contains very high proportion of free calcium. For the same reason, calcium hydroxide should generally be avoided as an oxide component in the second precursor component. In one aspect, an alkaline precursor component may comprise wollastonite and Class F fly ash in an amount not to exceed more than three times that of the Mg(OH)2 or any oxide in the broadest range and two times in the specific range to provide a reasonably good shelf life.
- The disclosed compositions optionally may include one or more additives, such as fillers surfactants (anionic or cationic, amphoteric, or nonionic), plasticizers, settling agents, rheology modifiers and/or suspending agents, and/or anti-foamers.
- Suitable fillers include for example, wollastonite, talc, Class C or F fly ash, kaolin clay, kaolinite, meta kaolin, mullite, calcium aluminate minerals, calcium silicate minerals, aluminum silicate minerals, calcium aluminum silicate minerals, or mixtures thereof. Other fillers alone or in combination with the above may be used. In certain aspects, the weight ratio of the filler is between 1:0.05 to 1:6 to that of the second component. In certain aspects, the instant compositions can be essentially free of calcium silicates.
- Suitable anionic surfactants include, for example, perfluorooctanoate (PFOA or PFO), perfluorooctanesulfonate (PFOS), sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, alkyl sulfate salts, sodium lauryl ether sulfate (SLES), alkyl benzene sulfonate, and soaps or fatty acid salts. Suitable cationic surfactants include, for example, cetyl trimethylammonium bromide (CTAB), alkyl timethylammonium salt, cetylpyridinium chloride (CPC), polyethoxylated tallow amine (POEA), benzalkonium chloride (BAC), and benzethonium chloride (BZT). Suitable amphoteric surfactants include, for example, dodecyl betaine, cocamidopropyl betaine, and coco ampho glycinate. Suitable nonionic surfactants include, for example, alkyl poly(ethylene oxide), alkylphenol poly(ethylene oxide), poloxamers or poloxamines (copolymer of polyethylene oxide or polypropylene oxide), octyl glucoside, decyl maltoside, cetyl alcohol, oleyl alcohol, and dodecyl dimethylamine oxide. Other surfactants alone or in combination with the above may be used.
- Suitable plasticizers include, for example phthalates, trimellitates, aliphatic dibasic esters, phosphates, epoxides, or polyesters. Specific examples of plastizers include, for example, DOP (di(2-ethylhexyl) phthalate, DINP (di(isononyl) phthalate, TOTM (tris(2-ethylhexyl)trimellitate, TINTM (tris(isononyl)trimellitate, DOA (di(2-ethylhexyl) adipate, DINA (di(isononyl) adipate, DOZ (di(2-ethylhexyl) azelate, and DOS (di(2-ethylhexyl) sebacate. Other plastizers alone or in combination with the above may be used.
- Anti settling agents include, for example, soya-lacithin, aluminium stearate, stearate coated calcium carbonate, modified cater oil or fatty acids, dipentene, pine oil, methyl ethyl ketoxime, di-isobutylene-maleic dispersion, ammonium polyacrylate, modified soya lecithin emulsion, polycaprolactonepolyol-polyethyleneimine block copolymer, polycaprolactonepolyol-toluene diisocynate copolymer, polyhydroxystearic acid, and alkyd based anti settling agents. Other settling agents alone or in combination with the above may be used.
- Suitable rheology modifiers/suspending agents include hydrated magnesium aluminum silicate, lignosulfonates (calcium lignosulfonates, sodium lignosulfonates and the like), salts of sulfonated naphthalene sulfonate condensates, salts of sulfonated melamine sulfonate condensates, beta naphthalene sulfonates, sulfonated melamine formaldehyde condensates, naphthalene sulfonate formaldehyde condensate resins, for example, LOMAR D® dispersant (Cognis Inc., Cincinnati, Ohio), polyaspartates, oligomeric dispersants, polymethacrylate salts, guar gum, diutan gum, welan gum, xanthan gum and/or other agents that function as a rheology modifiers/suspending agent. It has been observed that certain rheology modifiers/suspending agents, for example, DARVAN (sodium polymethacrylate) can provide only limited performance, e.g., providing smooth coatings at only about 15% of Al2O3 or other similar high density particles. Thus, the particular choice of rheology modifiers/suspending agent in not predicable for any particular phosphate ceramic formulation.
- Anti-foamers include, for example, silicon based anti-foam oil (siloxane with polyether terminal groups), acetylene glycol surfactants, and poly octyl acrylates. Other anti-foamers alone or in combination with the above may be used.
- Phosphates are nutrients for algae and hence one should expect algae growth in the acidic component. To avoid algae, one can add various commercial additives that inhibit any biological activity. One good example is cupric oxide. The addition of less than 1 wt. % of cupric oxide in the acidic phosphate precursor is sufficient to inhibit biological growth. Other commercial chemicals used to prevent algae or fungal growth may also be used.
- Disclosed and described herein are novel inorganic two component precursor formulations comprising acid phosphates, oxychloride, and oxysulfate solutions and pastes, and a basic component comprising oxides and hydroxides, that can be brought together to react instantly so that the resulting product is an inorganic (oxychloro-) or (oxysulfo-)phosphate composition. Methods of producing the two acid and base components and their combinations, atomizable sprayable formulations, and optionally a substantially amorphous, reduced crystallinity ceramic are disclosed and characterized as set forth in the following selected examples, but the methods and claims are also applicable to other acid-base formulations with suitable modification of the components such as oxychloride and oxysufate systems. A brief discussion on these modifications is provided, but that discussion is not intended to limit the claims or the disclosure itself.
- Several examples, listed below, were conducted in order to formulate and demonstrate the attributes of the compositions disclosed herein.
- In this experiment, the first (acidic) component consisted of mono potassium phosphate (MKP) having a pH of about 4.2 when measured in aqueous solution. The MKP was milled for an hour prior to use to about 74 micron size powder (US 200 sieve). The MPK was then further milled for an hour and Its pH was adjusted between 3.2 and 3.5 by adding 2.5 wt. % phosphoric acid (added as 50% dilute solution). 0.5 wt. % cupric oxide was added to prevent algae growth. The solution was adjusted with water to yield a viscosity of approximately 10,000 centipoise. The density of this component was 1.9 g/cm3.
- The second component (alkaline) was prepared as follows: A requisite amount of magnesium brine solution (Martin Marietta), as a source of magnesium hydroxide, was weighed into a mixer. Zr(OH)4 powder was added to the brine and stirred for 5-10 min until homogenous. Wollastonite passing 325 mesh was added slowly to this solution and mixed for 10-15 min. An additional amount of water was added to adjust the viscosity to approximately 20,000 to 25,000 centipoise. The density of this liquid component was 1.25 g/cm3 and the average particle size of particles in this solution was determined to be about 5.6 micrometers or less. Thus, the second component consisted of about 69 wt. % magnesium brine (providing about 61 wt. % Mg(OH)2), about 8.7 wt. % wollastonite, about 2.2 wt. % zirconium hydroxide (Zr(OH)4), the remainder water.
- The two components were combined in the volume ratio of 1:1 for spray using a plural spray system. The two cartridges of the spray system were filled separately with the two components. The spray gun consisted of a mixing tube, in which the two components could be mixed prior to spraying. The composition was sprayed on different substrates e.g., steel, wood, hardboard, aluminum, concrete, mild steel Taber panels. The thickness coated was approximately 15-20 mil. Abrasion resistance measurements were made according to ASTM D 4060. The coatings were allowed to cure at ambient conditions for 7 days before all tests and sample analyses were done.
- The resultant films of the inorganic phosphate composition disclosed herein were compared with commercial epoxy coating and a conventional inorganic phosphate concrete (Ceramicrete) coated on mild steel panels. The results of density, adhesion (pull out test, ASTM D4541), and abrasion resistance are summarized in Table 2 below.
-
TABLE 2 Test results on the magnesium potassium phosphate composition Wear Index Adhesion (wt. loss per Density resistance Wear cycle in Coating system (g/cm3) (psi) cycles/mil micrograms) MKP coating 1.4 334 423 118 without colloidal silica MKP with 1.4 226 528 105 colloidal silica Epoxy coating 1.2 120 120 300 CONTROL 1.8-2.0 (Ceramicrete) - The results in Table 2 show that the density of the coatings is close to commercial organic coatings. Magnesium hydroxide has a lower density (2.38 g/cm3) compared to the density of calcined magnesium oxide (periclase), which is 3.6 g/cm3. For regular Ceramicrete (phosphate cement), produced from calcined magnesium oxide, the density is between 1.8 to 2 (g/cm3) depending on the fillers used. Thus, regular Ceramicrete is heavier than the inorganic phosphate composition disclosed herein. In Ceramicrete, most calcined magnesium oxide remains unreacted as suspended or embedded particulate matter, which contributes to the density. In contrast, the density of the inorganic phosphate composition disclosed herein is less than that of Ceramicrete, which is believed due to more complete reaction of magnesium hydroxide source and the reduced amount of particulate magnesium oxides. As a result, the inorganic phosphate compositions disclosed and described herein result in lower density materials, for example, densities of about 1.4 g/cm3, which are comparable to organic coatings. In contrast, densities of typical organic phosphate cements of similar composition prepared from periclase are between 1.8 to 2.0 g/cm3.
- Magnesium hydroxide has a hexagonal platelet or sheet structure that is structurally and morphologically different from calcined magnesium oxide (periclase) that has a cubic structure. In addition to lower density inorganic phosphate compositions, it is believed that the sheet structure of magnesium hydroxide resultant inorganic phosphate compositions derived therefrom provide smoother coatings and superior abrasion resistance compared to coatings prepared from calcined magnesium oxide derived inorganic phosphates. The average particle size difference of the resultant inorganic phosphate compositions derived from magnesium hydroxide (greater than 5 m2/g) as disclosed and described herein also contributes to the superior abrasion resistance and smoothness of the coatings verses those of calcined magnesium oxide (less than 0.55 m2/g).
- The data in Table 2 also demonstrates that the inorganic phosphate composition disclosed herein is far superior to the epoxy coatings. For example, the inorganic phosphate composition has an adhesion resistance two to three times that of commercial epoxy coating, wear test results are about one fourth that of epoxy, and wear index, which represents wear loss, is about one third that of epoxy coating. Thus, the inorganic phosphate compositions disclosed herein are far superior to some commercial coatings available in the market.
- Powder X-Ray Diffraction Comparison of the Organic Phosphate Composition Disclosed Herein with Conventional Phosphate Concrete
-
FIG. 1 below shows the X-ray diffraction patterns of two identical samples prepared as described in Example 1, one sprayed as a thin coat and the other sprayed as a thick coat (marked as “A”). Both coatings exhibit exactly the same pattern, indicates that the coating formulation as in Example 1 may be used either as thin or thick coating. The main peaks ofFIG. 1 represent CaSiO3, Mg(OH)2 and MgKPO4.6H2O. Each peak, however, is broadened. Breadth of an x-ray diffraction peak is indicative of amorphous or microcrystalline phases. For comparison, the X-ray diffraction pattern of Ceramicrete, a chemically similar phosphate cement produced by calcined magnesium oxide, is reproduced inFIG. 2 overlaid with that of a sample Example 1. The data shows the corresponding peaks of the sample from Example 1 are broader than in Ceramicrete, which indicates that the amorphous content (reduced crystallinity) inorganic phosphate composition disclosed herein is substantially higher than in Ceramicrete. The data inFIG. 2 also shows that in the Ceramicrete, the calcined magnesium oxide peak is substantially larger than that of the inorganic phosphate composition disclosed herein, which indicates that a significant amount of magnesium oxide remains unreacted or in macrocrystalline form in the Ceramicrete. Thus, the reaction of oxide in the inorganic phosphate composition as disclosed herein is likely more complete and/or the amount of crystalline oxide is substantially reduced, resulting in a substantially reduced crystallinity product suitable for coatings. - 30 g of aluminum hydroxide (gibbsite, Al(OH)3) were added at room temperature to 173.4 g of phosphoric acid solution (H3PO4, 50 wt. %, molar ratio Al(OH)3:H3PO4=1:2.3). 1.5 g (5 wt %) of potassium fluoride, and 1.5 g of potassium permanganate were added to the acid together with Al(OH)3. The mixture was stirred for 60 min to about 3 hours at 100-110° C. The resultant product after cooling to room temperature was a viscous paste. This was labeled acid component A.
- Potassium permanganate, as an exemplary oxidizer, was added as an optional reagent to reduces hydrogen formation in Example 2. Use of an oxidizer provides improved adhesion to surfaces, such as steel/iron surfaces. Results of coatings of the composition of Example 2 on steel/substrates provided improved adhesion between the inorganic phosphate composition and the metal compared to its adhesion in the absence of the oxidizer. Other suitable oxidizers may be used, for example, water soluble oxidizers, such as potassium chromate, sodium chromate, or nitrates of potassium, magnesium, and aluminum.
- The X-ray diffraction pattern in
FIG. 3 shows that aluminum hydroxide, which is fairly crystalline, when mixed with phosphoric acid solution in the process described above, provides a less crystalline form of the aluminum hydroxide as evidenced by the broad halo pattern. In conventional phosphate cements, such an amorphous, non-crystalline phase is insignificant or non-existent (not shown). The amorphous component A results in clear honey-like paste. This may be seen in photographs given inFIG. 4 . These were produced with different concentration of aluminum hydrophosphates, but all produce transparent thick gels. - The basic component was produced by mixing wollastonite and MgO in the weight ratio of 3:1 in sufficient water to produce precursor with approximate viscosity of 10,000 centipoise. Similarly, in another experiment, mullite was added instead of wollastonite. The basic component was labeled B. The basic component may be magnesium brine having an effective amount of magnesium hydroxide.
- The two components (A+B) were mixed in a weight ratio of 8:3, and the resultant precursor composition was coated on various substrates that included mild steel, aluminum, wood, and cement board. The samples were allowed to cure for one week.
FIG. 5 shows the X-ray diffraction pattern of the coating along with that of wollastonite and the first acidic phosphate component for comparison. - Similarly,
FIG. 6 shows the X-ray diffraction pattern of the coating produced with mullite and Part A, and also a mixture of mullite and magnesium oxide as Part B and aluminum hydro phosphate. All samples were very hard and bonded well to various substrates. The resultant coatings could not easily be scratched and could not be dislodged, even when the substrate was hit against a hard object. - Comparison of the components and the set coating in
FIGS. 5 and 6 demonstrate that, though highly crystalline mullite, wollastonite, and magnesium oxide were used as starting materials, the x-ray diffraction peaks associated with these crystalline materials in the set inorganic phosphate composition were substantially reduced in height and were broader than the individual constituents. Thus, the crystallinity of the set inorganic phosphate composition is substantially reduced. While not being held to any particular theory, it is believed that the acidic component is at least partially responsible for developing and or providing this reduced crystalline morphology for the inorganic phosphate composition disclosed and described herein. -
FIG. 7 shows these final coatings as sprayed in plastic cups. They all are homogeneous in appearance, smooth on the surface, and dense. Regular Ceramicrete does not exhibit these unique properties, at least because it lacks the reduced crystalline morphology that this present embodiment of the inorganic phosphate compositions disclosed herein have. - Theoretical analysis based on thermodynamic principles indicate that aluminum trihydrogen phosphate, if reacted with aluminum oxide (corundum, Al2O3), would produce aluminum phosphate (AlPO4) (berlinite) at about 150° C. Berlinite mineral phase, which is stable up to 1,500° C., would provide a high-temperature coating. Thus, 100 grams of aluminum trihydrogen phosphate (AlH3(PO4)2.5H2O) viscous paste as disclosed in Example 2, was mixed with 50 grams of aluminum oxide fine powder and mixed thoroughly to form a thick paste. This was brushed on mild steel substrate pre-heated at 175° C. Initially, some water fraction from the paste evaporated, but the subsequent coating bonded well to the steel. The entire assembly was maintained at 175° C. for about three hours. Once all degassing and evaporation had occurred, a second coat was applied and cured for about three hours at 175° C. The resulting thick coating formed on the steel surface was hard, dense and extremely well bonded to the steel. X-ray diffraction studies of the formed coating prepared from Example 3 indicated that the coating was essentially berlinite. Thus, the methods disclosed and described herein provides for a relatively simple means for preparing berlinite-precursor formulations and thereafter forming berlinite coatings useful for providing high-temperature protection or improving high temperature service of articles, such as metals and other building materials.
- In this example, alkaline component comprising 55 wt. % brine, 22 wt. % Class F fly ash, 6 wt. % zirconium hydroxide, 14 wt. % water, and 3 wt. % commercial paint conditioner. All components were mixed thoroughly to a form paste of approximate viscosity 10,000 centipoise. The acidic component was prepared as a paste by mixing 68% mono potassium phosphate and 31 wt. % water, a small amount of a suspension agent and cupric oxide to prevent formation of algae.
- The two component solutions were used in a plural spray gun at a volume ratio of acidic to alkaline components of 1:1.5. They were sprayed on mild steel plates and standard plates used for abrasion tests. After curing the plates with coatings were tested for abrasion resistance and adhesion in accordance with ASTM protocol. The average values of the results on three different samples as well as a commercial epoxy coating control are given below in Table 3.
-
TABLE 3 Test results on Example 4 compared to epoxy control. Wear Index Adhesion (wt. loss per cycle Coating system resistance (psi) Wear cycles/mil in micrograms) Fly ash-containing 180 360 154 coating Epoxy coating 120 120 300 CONTROL - The results shown in Table 3 demonstrate that in all respects, the inorganic phosphate composition coating comprising fly ash showed better abrasion and wear performance compared to the epoxy control coating. The adhesion resistance is approximately 50% higher, and abrasion performance is at least twice that of epoxy coating. This shows that the inorganic phosphate composition coating comprising fly ash coatings are superior to commercial epoxy coatings.
- In this Example, the same composition as in Example 4 was prepared with the exception that instead of fly ash, mullite (3Al2O3.2SiO2) in fine powder form was used instead. The proportion of the two components (acidic phosphate/basic hydroxide) was the same as Example 4 and samples were prepared by spraying on mild steel and abrasion plates. The results of these tests are given in Table 4.
-
TABLE 4 Test results on Example 5 coating compared to epoxy Control Wear Index (wt. Adhesion loss per cycle in Coating system resistance (psi) Wear cycles/mil micrograms) Mullite-containing 143 337 157 coating Epoxy coating 120 120 300 CONTROL - As in the case of Example 4, the results of Example 5 show that in all respects, the inorganic phosphate composition coating comprising mullite also shows improved performance characteristics compared to the epoxy control coating. The adhesion resistance of Example 5 is approximately 20% higher, and abrasion performance is at least twice that of epoxy coat. This shows that fly ash coatings are not only viable but are far superior to commercial coatings.
- The first (acidic) component consisted of mono potassium phosphate (MKP) having a pH of about 4.2 when measured in aqueous solution. Calcium phosphate precursor can also be used. The MKP powder (about 74 micron size US 200 sieve) was added and the solution pH was adjusted between 3.2 and 3.5 by adding 2.5 wt. % phosphoric acid (added as 50% dilute solution). 0.5 wt. % cupric oxide was optionally added to prevent algae growth. The solution was adjusted with water to yield a viscosity of about 10,000 centipoise. The density of this component (component A) was about 1.9 g/cm3.
- The second component (alkaline) was prepared as follows: A requisite amount of magnesium brine solution (Martin Marietta), as a source of magnesium hydroxide, was weighed into a mixer. Zr(OH)4 powder was added to the brine and stirred for 5-10 min until homogenous. Wollastonite passing 325 mesh was added slowly to this solution and mixed for 10-15 min. An additional amount of water was added to adjust the viscosity to approximately 20,000 to 25,000 centipoise. The density of this liquid component was 1.25 g/cm3 and the average particle size of particles in this solution was determined to be about 5.6 micrometers or less. Thus, the second component consisted of about 69 wt. % magnesium brine (providing about 61 wt. % Mg(OH)2), the remainder water. The MgOH brine can be substituted with MgO, preferably calcined MgO. The following are examples of high solids loading phosphate precursor components suitable for spray coating that can be atomized to provide thin film, paint-like coatings. These examples use solids of Part A (e.g., MKP) and Part B (e.g. MgO). Substitutions of either Part as described above is envisaged. Table 5 summarizes exemplary atomizable compositions (Sample 1 & 2).
-
TABLE 5 Atomizable Compositions % Viscosity Density Suspension solids (cp) (g/cc) pH agent wt % Sample Part A ~73% ~30,000+ ~2.2 3.3 0.15-1.5 1 Part B ~60% ~25,000+ ~2.0 10.4 Sample Part A ~63-64% ~14,000 ~1.55 3.3 0.15-1.5 2 Part B ~54% ~13,000 ~1.5 10.4 - Sample 3: To an amount of water, to which is added a required amount of 85% phosphoric acid, is added the acid phosphate precursor (e.g. monopotassium phosphate (MKP)) and mixed for less then a minute, followed by the addition of the suspension agent (e.g., xanthan gum) with mixing for 10 minutes with a high shear dispersion blade. The water-phosphate mixture will become thick and change color to opaque, then add required amount of MKP to the suspension. In the above Samples (1 and 2) about 1 to 60 wt % resin coated silica (Estes Colored Aggregates obtained from Clifford Estes Company, Fairfield, N.J.; particle sized between about 30-70 mesh) can be distributed all in one component Part or distributed (equally or non-equally) in either component Part. Aggregate colorant of 30-325 mesh size at a wt % solids loading of abut 1 to 60 is also useful in the instant formulations. Preferably, the Estes colored aggregates can be added to Part A at a level of about 0-30 wt % solids or more. In at least one example, 6 wt % of Estes colored aggregates was used in the
above Sample 2 and provided excellent color and appearance in the final coating. It has also been observed that colored art sand or naturally colored sand and aggregate can be employed with similar results. In the above Samples, about 0.2 wt % xanthan gum was used as suspension agent, (about 0.05 wt % used in Part B). The two components were combined in the volume ratio of 1:1 for spray using a plural spray system having a peristaltic pump. Similar results can be achieved using high pressure piston pumps (airless spray) that provide high pressure to atomize. Alternatively a multi-channel pump, a plural piston pump, a ram discharge extruder, a two-component caulking gun or a progressive cavity pump with static mixing and air-assist for atomizing can be used. The two cartridges of the spray system were filled separately with the two components. The spray gun consisted of a mixing tube, in which the two components could be mixed prior to spraying. The composition was sprayed on different substrates e.g., steel, wood, hardboard, aluminum, concrete, mild steel Taber panels. The thickness coated was approximately 5 mil and had a noticeable color from the aggregate colorant. Coatings up to about 20 mil are achievable using the method disclosed herein. The coatings were allowed to cure at ambient conditions and resulted in excellent coatings with phosphate cement characteristics. In contrast, ordinary sprayed paint required thin (<2 mils) to avoid run or sag that would not hold similar amounts of aggregate of any size. Thus, in one aspect, other non-ceramic, rapid set/cure coatings can employ such aggregates provided the coating thickness is at least 20 mil so as to provide some mechanical securing of the aggregate. - Moreover, unlike ordinary paint that takes a long time to dry allowing the aggregate to migrate from its initially deposited location and/or fall out before it can be “mechanically” held in place, the instant phosphate ceramic spray composition sets rapidly and at least mechanically holds the aggregate in place sufficiently to be sprayed on vertical surfaces and overhead surfaces without the aggregate migrating or falling out.
- In one aspect, the instant phosphate ceramic spray composition with resin coated silica aggregate does not substantially bind to the resin coating of the aggregate, thus improving the aesthetics of the coating, e.g., by not coating or covering portions of the resin coating, thus allowing the color of the aggregate to be visualized to a greater extent. This is augmented by the naturally semi-translucent appearance of a pigment-free phosphate ceramic resulting in a more vibrant color appearance.
- In another aspect, the instant phosphate ceramic spray coating can comprise other aggregate to add texture. In another aspect, the instant phosphate ceramic spray coating can comprise non-colored natural aggregate (e.g., sand, talc, etc.) to give natural finish, for example, a sand plaster type finish in a single color.
- In another aspect, the instant phosphate ceramic spray composition is used as a primer layer for a substrate, for example, a metal surface, and is subsequently coated with a polymer coating such as an acrylic or urethane coating. The metal surface can be a transportation vehicle for example, a chassis. If desired, aluminum oxide can be added to either or both of the first and second components in an amount sufficient to increase the hardness of the resultant phosphate ceramic.
- While the above aggregate phosphate ceramic composition is disclosed as useful for a spray system, the same textured and/or colorant composition is suitable for application by non-spraying coating methods, such as by trowel, etc.
- All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification may be to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth herein may be approximations that may vary depending upon the desired properties sought to be obtained.
- The above description discloses several methods and materials. These descriptions are susceptible to modifications in the methods and materials, as well as alterations in the fabrication methods and equipment. Such modifications will become apparent to those skilled in the art from a consideration of this disclosure or practice of the disclosure. Consequently, it is not intended that this disclosure be limited to the specific embodiments disclosed herein, but that it cover all modifications and alternatives coming within the true scope and spirit of the claims.
Claims (15)
1. An atomizable phosphate ceramic spray system comprising
a first component cartridge comprising an aqueous solution of an acid-phosphate of chemical formula Am(HPO4)m.nH2O, where A is hydrogen ion, ammonium cation, metal cation, or mixtures thereof; where m=1-3, and n=0-6; the first component solution adjusted to a pH of about 2 to about 5;
a second component cartridge comprising an aqueous solution of an alkaline oxide or alkaline hydroxide represented by B2mOm, B(OH)2m, or mixtures thereof, where B is an element of valency 2m (m=1, 1.5, or 2) the second component solution adjusted to a pH of between 9-14; and
optionally, a rheology modifier/suspending agent in an amount capable of providing shear thinning of either the first component or the second component and further capable of suspending a high solids content of either the first component or the second component for atomization; and
high shear dispersion blade; and
a plural sprayer operably connected to a pump.
2. The phosphate ceramic spray system of claim 1 , wherein the second component is at least one of magnesium hydroxide and calcium hydroxide, and water.
3. The phosphate ceramic spray system of claim 1 , wherein the first component comprises about 2 to about 10 wt % phosphoric acid, water, and at least one of mono potassium phosphate and mono calcium phosphate.
4. The phosphate ceramic spray system of claim 1 , further comprising aluminum oxide present in an amount sufficient to increase the hardness of the phosphate ceramic.
5. The phosphate ceramic spray system of claim 1 , wherein the rheology modifier/suspending agent is at least one of guar gum, diutan gum, welan gum, and xanthan gum.
6. The phosphate ceramic spray system of a claim 5 , wherein the aggregate is present in an amount of at least about 1 wt % to about 60 wt %.
7. The phosphate ceramic spray system of claim 6 , wherein the aggregate is at least one of a resin coated silica and a naturally colored mineral aggregate.
8. The phosphate ceramic spray system of claim 6 , wherein the aggregate is of an average particle size of about 20 mesh micron to about 400 mesh.
9. The phosphate ceramic spray system of claim 6 , wherein the aggregate is of an average particle size of at least about 20 mesh or less and, after application of a coating of less than about 20 mil, substantially retains the aggregate in the coating on a vertical surface or an overhead surface.
10-48. (canceled)
49. An inorganic phosphate compound of the general formula:
i) Bs(A3-mPO4)s; wherein A has a valency of m=1 or 2; and B has a valency of s=1, or 2;
ii) Bs(A(2/m))PO4)s; wherein A has a valency of m=1 or 2; B has a valency of s=1, or 2;
iii) (2/m)A 3Bm(PO4)2; wherein A has a valency of m=1 or 2; B has a valency of 3; or
iv) B(AOPO4)s; wherein A has a valency of 4 and s=1 or 2; and B has a valency of 1, or 2;
wherein the inorganic phosphate i-iv has at least one of the following characteristics:
a) a substantially reduced amount of calcined alkali/alkali earth oxide particles present as measured b x-ray diffraction; or
b) a reduced crystalline morphology as measured by x-ray diffraction relative to a compositionally similarly inorganic phosphate ceramic or ceramic or,
c) a reduced density, relative to a compositionally similarly inorganic phosphate ceramic.
50. The inorganic phosphate compound of claim 49 , wherein the density is less than 1.8 g/cm3.
51. The inorganic phosphate compound of claim 49 , wherein the density is less than 1.5 g/cm3.
52. The inorganic phosphate compound of claim 49 , wherein the compound is at least one ofthe following: MgKPO4; Mg(ZnPO4)2Mg(K2PO4)2; Mg2KPO4; Mg(ZnPO4)2; Mg(K2PO4)2; Al2Mg3(PO4)2; Mg(ZrOPO4)2; Mg[Zr(OH)2PO4)2]2; and calcium/magnesium phosphate.
53-64. (canceled)
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- 2010-12-10 WO PCT/US2010/059958 patent/WO2011072262A2/en active Application Filing
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EP2509927B1 (en) | 2020-07-08 |
CA2783723C (en) | 2019-01-15 |
EP2509927A2 (en) | 2012-10-17 |
US8858702B2 (en) | 2014-10-14 |
JP2013513703A (en) | 2013-04-22 |
CN102781871A (en) | 2012-11-14 |
AU2010327923B2 (en) | 2015-05-07 |
WO2011072262A2 (en) | 2011-06-16 |
ES2821489T3 (en) | 2021-04-26 |
JP6134140B2 (en) | 2017-05-24 |
CN102781871B (en) | 2014-11-26 |
KR20120113224A (en) | 2012-10-12 |
AU2010327923A1 (en) | 2012-07-26 |
US20160068442A9 (en) | 2016-03-10 |
EP2509927A4 (en) | 2013-07-24 |
CA2783723A1 (en) | 2011-06-16 |
WO2011072262A3 (en) | 2011-10-13 |
US20110143910A1 (en) | 2011-06-16 |
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