CN108219680A - For the adhesive composition of sclerotin historical relic reparation - Google Patents
For the adhesive composition of sclerotin historical relic reparation Download PDFInfo
- Publication number
- CN108219680A CN108219680A CN201711345477.3A CN201711345477A CN108219680A CN 108219680 A CN108219680 A CN 108219680A CN 201711345477 A CN201711345477 A CN 201711345477A CN 108219680 A CN108219680 A CN 108219680A
- Authority
- CN
- China
- Prior art keywords
- component
- historical relic
- phosphate
- adhesive composition
- sclerotin
- 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.)
- Pending
Links
- 108010048734 sclerotin Proteins 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000000853 adhesive Substances 0.000 title claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 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 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical group [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims description 16
- 239000001506 calcium phosphate Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 8
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 8
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 8
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 102000008186 Collagen Human genes 0.000 claims description 4
- 108010035532 Collagen Proteins 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001436 collagen Polymers 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 108010022355 Fibroins Proteins 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 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 3
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 abstract description 15
- 230000032683 aging Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005728 strengthening Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 34
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 20
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 210000000988 bone and bone Anatomy 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000007767 bonding agent Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229960001714 calcium phosphate Drugs 0.000 description 6
- 235000011010 calcium phosphates Nutrition 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 235000019700 dicalcium phosphate Nutrition 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 241000241413 Propolis Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940036811 bone meal Drugs 0.000 description 1
- 239000002374 bone meal Substances 0.000 description 1
- 230000037118 bone strength Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229940069949 propolis Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J1/00—Adhesives based on inorganic constituents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of adhesive compositions for sclerotin historical relic reparation, including component A, component B, component C and the water mixed when in use, the component A is synthos curing agent, and the component B is toughening binding agent, and the component C is phosphate accelerating agent；Wherein, when preparing the adhesive composition, the proportioning of each component is as follows in parts by weight：4~8 parts of 100 parts of component A, component B, 2~4 parts of component C, 30~36 parts of water.Above-mentioned component is mixed in proportion and is mixed thoroughly; obtain the slurry of certain consistency; there is good bonding reinforcement effect to fragile and fracture sclerotin historical relic; its primary curing object is calcium hydroxy phosphate; it is identical with sclerotin historical relic main component; passing the shortcomings of using easy to aging and sclerotin historical relic ontology poor compatibility existing for organic high molecular polymer strengthening agent is overcome, meets the requirement of historical relic's protection.
Description
Technical field
The present invention relates to a kind of adhesive materials, particularly a kind of adhesive composition for sclerotin historical relic reparation.It should
Adhesive composition may be widely used for the reparation of the sclerotin historical relic in historical relic's protection reparation field.
Background technology
With the continuous development of technology, the human skeletal of Unearthed when Archaeological Studies and collection, all kinds of animal skeletons and bone object are research
The important foundation in kind of human development history and nature developing history, has high researching value.Sclerotin historical relic for a long time by
The influences such as itself composition, natural environment and human factor, inevitably occur microbial degradation and chemical degradation.With organic
The loss of matter and gradually changing for inorganic structural, it is increasingly spacious inside sclerotin, fragile, and then cause to crack, peel off, crisp powder
Deng, it is necessary to it is protected and repairs.
Traditional sclerotin historical relic reinforcement material is mostly high molecular polymer, such as is most used in the world early in 19th century various
Natural resin such as shellac, natural gum, linseed oil, propolis, the nitrocellulose and polymer chemistry of the 1930s are vigorously sent out
The synthetic materials such as the polyvinyl alcohol, polyethylene glycol, all kinds of acrylic resins, the lotion that are born after exhibition.Wherein natural resin, natural
Grease, zapon have the characteristics that fast drying, hard wear resistant, but acid and alkali resistance, photooxidation aging property are relatively low, part reinforcement performance
It is bad, per se with reasons such as color, greasy feelings, be eliminated at present.Polyethylene glycol then easily in high humidity environment surface aggregation and
Adhering dust and reinforcement material should not be used as.Though cellulose ether has good resistance to ag(e)ing, its water resistance is very poor.Polyvinyl acetate
Color and luster is partially dark after ester is reinforced, Surface glare, while insufficient in terms of resistance to ag(e)ing, invertibity and water resistance.Polyvinyl alcohol contracting fourth
Aldehyde resistance to ag(e)ing is poor, fine for live temperature pier effect, but is also easy to produce white film, and poor permeability.Organosilicon material
Material sclerotin historical relic is carried out moisturizing, oxygen barrier, it is anti-mildew seal up for safekeeping, work well, can realize the purpose protected temporarily substantially, but seal
After depositing several years, organosilicon material will appear different degrees of color change, and the internal material for having substance exudation, aging is difficult to
It removes, effect is poor when being reinforced for being bonded.In recent years, because it is found that acrylic resin has excellent reinforcement performance and ageing-resistant
Property, domestic historical relic's protection worker are mostly used acrylic material, and wherein acrylic resin Paraloid B-72 are in dry sclerotin
Good result is obtained on historical relic；Acrylic emulsion Rhoplex AC-33, the characteristics of with its good penetrability, to aqueous osteoid
Historical relic consolidation effect is better than polyethylene glycol and polyvinyl acetate, but its glass transition temperature is low, and possible fastening strength is insufficient.Propylene
It is more preferable to reinforce sclerotin historical relic effect than AC-33 grain sizes smaller (about 30 μm), good penetrability by acid colloids Acrysol WS-24.This three
Although kind of acrylic resin air drying, strong adhesive force, the transparency are good, acidic-group can be generated after the aging of part, may be promoted
Into sclerotin heritage corrosion.
Although the performance of sclerotin historical relic's protection repair materials is constantly improving, but still has problems not yet fully to be solved
Certainly, above-mentioned various problems are that the essence of high molecular material determines that life expectancy is still far smaller than hydroxyapatite, are this add
Solid system is difficult to the obstacle gone beyond.The drawbacks of to overcome organic matter reinforcement protection, in recent years researcher employ hybrid material, change
The organic/inorganic composite materials such as property waterglass material or purely inorganic material protect Jinsha Gu ivory etc., the researchs such as Qiu Zehao
Organic-inorganic hybrid material prepared by sol-gel method, has prepared PMMA/SiO respectively2、HEC/SiO2、PVA/SiO2、
PDMS/SiO2Hybrid material etc., and filtered out preferable protection materials PDMS/SiO2It protects, achieves certain for ancient ivory
Effect, but there are after volume contraction, aging turn to be yellow discoloration the problems such as.Modified water glass material permeability is poor, and alkalinity is big, to bone
Collagen has destruction in matter historical relic, it is also possible to cause the crystal transition of hydroxyapatite in sclerotin historical relic, not meet
Repair principle.Another problem is when reinforcing large porosity historical relic and bonding fracture, defect historical relic during sclerotin historical relic is reinforced, need to be
Solid packing is added in strengthening agent, solid packing is resistance to old although the service life is longer than organic matter mostly using inorganic matters such as mountain flour, bone meal
It is good to change performance, but itself is without intensity, reduces adhesive strength after being mixed with strengthening agent, it is also possible to lead to the problem of and expand with heat and contract with cold.
Solve the problems, such as that these need to break through conventional thought, from most root problem on, fresh sclerotin mainly include machine into
Divide (accounting for about 35%) and inorganic constituents (accounting for about 65%).Organic substrate is made of collagenous fibres；Inorganic matrix is mainly hydroxyl phosphorus
Lime stone.Inorganic matrix provides bone hardness and pressure, and the collagenous fibres in organic substrate provide support and tension.Hydroxyapatite
Heart crystallographic axis is parallel with collagenous fibres long axis, and this composite construction makes bone tissue have both intensity and toughness simultaneously.This is any
What homogenous material was unable to reach, therefore, support of the bone as life entity, be it is a kind of with high intensity, high tenacity inorganic and
Organic composite material, the Nomenclature Composition and Structure of Complexes of itself are deciding factors.Child's good toughness, but its bone strength it is low be because
Hydroxyapatite not yet forms orderly crystal；The elderly's sclerotin is loose, easily fractures, and is by the loss of calcium and shortage institute
It causes.The different degrees of loss of organic matter, hydroxyapatite content are increased to more than 70% in the sclerotin historical relic of weathering.Doctor at present
Start to fill defect of human body bone position with hydroxyapatite on, be more to consider biocompatibility other than reinforcing and supporting.
In sclerotin historical relic's protection field, if using sclerotin material itself or similar material, the structure of similar bone is formed to reinforce sclerotin
Historical relic, undoubtedly a kind of very promising research direction because with own material come reinforcement protection historical relic, have with it is other
The unrivaled advantage of material, has obtained being widely recognized as historical relic's protection worker, consistent due to material physical chemistry property：
(1) other chemical compositions will not be introduced, additional substance will not be generated after aging, reduce that historical relic is contaminated and erosion is asked
Topic；(2) digestion period matches, and avoids the secondary injury that ontology and reinforcement material differ digestion period；(3) it is asked without compatibility
Topic, the variation of external environment will not generate stress, will not lead to the problem of dry and wet interface；(4) it is not required to consider going for reinforcement material
Except problem, reprocessing property fundamentally ensure that；(5) aging rule is identical, it is contemplated that the service life.
If in conclusion developing the proper constituent of historical relic into historical relic protection materials, other materials can be avoided to be difficult to
Some defects solved have unique development prospect, but single use hydroxyapatite, since intensity is low, can not play and add
Gu effect, therefore need to be improved.
Invention content
In view of the above problem of the existing technology, the object of the present invention is to provide a kind of for the viscous of sclerotin historical relic reparation
Mixture composite.The adhesive composition may be widely used for the reparation of the sclerotin historical relic in historical relic's protection reparation field.
To achieve these goals, technical solution proposed by the present invention is：Gathered using calcium phosphate mineral and organic polymer
The organic-inorganic composite body that object is compound, and formation compression strength is high, cementability is strong is closed, setting time is adaptable with repairing operation, Gu
Final product is mainly calcium hydroxy phosphate after change, and identical with the inorganic component in sclerotin historical relic, composite structure is close with sclerotin.
Specifically, a kind of adhesive composition for sclerotin historical relic reparation provided in an embodiment of the present invention, being included in makes
Component A, component B, component C and the water of used time mixing, the component A are synthos curing agent, and the component B is bonded for toughening
Agent, the component C are phosphate accelerating agent；Wherein, when preparing the adhesive composition, the proportioning of each component in parts by weight
It is as follows：
Preferably, the component A is mixed by two or more synthos, hybrid mode is with alcohol
For medium, fineness is milled in planetary mills less than 10 μm, then dry.
Preferably, the synthos are tricalcium phosphate, tetracalcium phosphate, calcium dihydrogen phosphate, calcium phosphate dibasic anhydrous or hydroxyl
Base calcium phosphate.
Preferably, it is characterized in that, the alcohol is absolute ethyl alcohol.
Preferably, the component B is selected from：Collagen, gelatin, fluorocarbon resin, polyvinyl alcohol, acrylic resin, silk
Fibroin, chitosan, polylactic acid, serine, polyethylene glycol, polyacrylamide, fluorine carbon emulsion, silicone acrylic emulsion, polyvinyl alcohol contracting
One or more in butyraldehyde, polyvinyl alcohol, carboxymethyl cellulose or hydroxypropyl methyl cellulose mix, and when mixing uses
Solvent is distilled water.
Preferably, the component C is mixed by two or more phosphate, mixed solvent is distilled water.
Preferably, the phosphate for sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate or
Potassium dihydrogen phosphate.
Preferably, the adhesive composition is made by following steps：
Step 1, liquid phase component is prepared, liquid solution is made by solvent of distilled water respectively in component B and component C；
Step 2, component A, component B and component C are mixed according to weight.
Compared with the prior art, there are following advantages provided by the present invention for the adhesive composition of sclerotin historical relic reparation：
(1) synthos curing agent main chemical compositions are identical with sclerotin historical relic bulk material, avoid due to material object
To historical relic bulk erosion, poor compatibility caused by Physicochemical property is different, the problem of digestion period differs, will not attract a large amount of
Foreign substance ensure that reprocessing property.
(2) inorganic calcium phosphate mineral hydrolyzable generation hardenite is organic viscous as skeletal support in synthos curing agent
Fragile and fracture ontology can be glued, and have certain toughness by connecing agent, overcome that sclerotin historical relic brittleness is had a surplus, toughness is insufficient and easily broken
The problem of splitting；The two learns from other's strong points to offset one's weaknesses to form the mechanical characteristics of similar fresh bone.
(3) inorganic calcium phosphate and water-soluble organic non-toxic material have been used, water is solvent, environment-protecting and non-poisonous, no organic volatile
Object, it is nonflammable.
(4) initial set and final setting time adapt to operation requirement and can be adjusted according to actual conditions.
Description of the drawings
Fig. 1 is the 3 days cured products and hydroxyl of the embodiment 1 of the adhesive composition for sclerotin historical relic reparation of the present invention
Base apatite XRD spectrum compares；
Fig. 2 is 3 days cured product microscopic appearances (5000 times) of embodiment 1；
Fig. 3 is the 3 days cured products and hydroxyl of the embodiment 2 of the adhesive composition for sclerotin historical relic reparation of the present invention
Base apatite XRD spectrum compares；
Fig. 4 is 3 days cured product microscopic appearances (5000 times) of embodiment 2；
Fig. 5 is the 3 days cured products and hydroxyl of the embodiment 3 of the adhesive composition for sclerotin historical relic reparation of the present invention
Base apatite XRD spectrum compares；
Fig. 6 is 3 days cured product microscopic appearances (5000 times) of embodiment 3.
Specific embodiment
Technical scheme of the present invention is further described in detail below in conjunction with attached drawing.
The imagination of the present invention is that the hydroxyapatite crystal of some strength is generated by the hydrolysis of calcium phosphate mineral, together
When, it has a surplus and the characteristics of brittleness is big, cementability is poor, is improved by compound organic matter, and pass through for product compression strength
It adds in curing agent and adjusts setting time, to meet operation requirement.
Specifically, a kind of adhesive composition for sclerotin historical relic reparation provided in an embodiment of the present invention, being included in makes
Component A, component B, component C and the water of used time mixing, the component A are synthos curing agent, and the component B is bonded for toughening
Agent, the component C are phosphate accelerating agent；Wherein, when preparing the adhesive composition, the proportioning of each component in parts by weight
It is as follows：
Wherein synthos curing agent A is tricalcium phosphate (TCP), tetracalcium phosphate (TTCP), calcium dihydrogen phosphate (MCPM), nothing
Two or more component in the synthos such as water calcium monohydrogen phosphate (DCPA), calcium hydroxy phosphate (HA) is in certain mass ratio
Mix, it is preferred to use manner of formulation be 70.73%TTCP+26.27%DCPA+3%HA.In some embodiments
In, it is possible to use other manner of formulation, for example, 75%TCP+20%TTCP+5%DCPA.Those skilled in the art can manage
Solution, the manner of formulation is merely illustrative, does not do concrete restriction to technical solution of the present invention.Those skilled in the art can also do
It is appropriate to change to realize technical scheme of the present invention.
(1) preparation method of phosphate firming agent:
Raw material particle size requirement：By taking calcium hydroxy phosphate as an example, optional worked materials or the nano material purchased in market less than 50nm can
Absolute ethyl alcohol is selected as medium, fineness can be milled in planetary mills less than 10 μm, then 100 DEG C of drying.Particularly with TCP, TTCP,
For MCPM, DCPA, the row drying again less than 10 μm is ground to alcohols, is relatively preferred mode of operation.
When the synthos to two kinds or more mix, can carry out in accordance with the following steps：Each group is weighed in proportion
Material is divided to be respectively charged into agate spherical tank, adds in appropriate absolute ethyl alcohol, the ground and mixed in horizontal planetary ball mill, 300 turns/
Min mixes 4h, takes out in 80 DEG C of drying.
And for the component B of the present invention, specifically, toughening bonding agent is chosen as collagen, gelatin, fluorine carbon tree
Fat, polyvinyl alcohol, acrylic resin, fibroin albumen, chitosan polylactic acid, serine, polyethylene glycol；Gelatin；Polyacrylamide；
Fluorine carbon emulsion；Silicone acrylic emulsion；Polyvinyl butyral；Polyvinyl alcohol；Carboxymethyl cellulose；In hydroxypropyl methyl cellulose etc.
One or two mix, and solvent is distilled water, and the polymer formed by solvent volatilization or hydrolysis fills calcium phosphate
Hydrated product gap, the hydroxyl contained, amino isopolarity group and inorganic hydroxyapatite have good adhesive force and bonding force,
Compound reduces the brittleness of firming body, improves flexibility and cementability.Recommend silicone acrylic emulsion, silicone acrylic emulsion be by containing
The organic silicon monomer of unsaturated bond adds in suitable auxiliary agent with acrylic monomer, and coating polymerization technique by nucleocapsid is polymerized
Lotion, combine organosilicon fire-resistant, weatherability, chemical-resistant, hydrophobic, surface can low not v ulnerability and acrylic acid
High colour retention, flexibility, the adhesion of resinoid.
Further, component C be phosphate accelerating agent, concretely sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate,
Two or more component in the phosphate such as potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate mixes, and is using solvent
Distilled water, the component are used to promote the hydrolysis of synthos powder, since the multistage hydrolysis of phosphate radical is in entire aquation system
The most complicated and maximum on the influence of hydration reaction degree, contain phosphate radical (PO so being used in liquid phase more4 3-) or phosphorus
Sour hydrogen radical (H2PO4 -、HPO4 2-) substance, adjust the process of hydration reaction by adjusting the ion concentration in aquation system.It pushes away
It is 0.25mol/L NaH to recommend the proportioning used2PO4+0.25mol/L Na2HPO4Or 0.30mol/L Na2HPO4+0.08mol/L
K2HPO4, can adjust setting time by increasing and decreasing dosage, meet and repair needs.
The adhesive composition for sclerotin historical relic reparation that the embodiment of the present invention proposes, is preferably matched when in use
System, step are as follows：
Step 1, liquid phase component is prepared, liquid solution is made by solvent of distilled water respectively in component B and component C；
Step 2, component A, component B and component C are mixed according to weight.
Specifically, when preparing the adhesive composition, the proportioning of each component is as follows in parts by weight：
Toughening consumption of binder is bigger, and the compression strength of firming body, tensile strength and adhesive strength are bigger, but organic components
The raising of content will reduce ageing-resistant performance, and the foreign substance of introducing is more, and the microstructure of firming body is had an impact more
Greatly.
Phosphate accelerator dosage is bigger, and setting time is shorter, otherwise longer, according to conventional reparation speed, dosage control
It makes in 2~4 grams/100 grams synthos curing agent, at room temperature, the presetting period, final setting time was at 20-40 points at 15-30 minutes
Clock.
On the one hand water plays dissolving peptizaiton as solvent, it is anti-on the other hand also to participate in hydrolysis as important reactant
Should, dosage directly affects the intensity of the consistency of initial stage slurry, setting time and firming body, and the big consistency of water consumption is low, is conducive to
Perfusion and penetration reinforcement to historical relic small gap, but can cause that setting time is elongated and firming body intensity is lower, in addition, its dosage
Also related with curing agent A granularities, the bigger dosage of granularity is smaller, and in practical operation, total dosage is suitable at 30~36 grams/100 grams
Phosphate firming agent curing agent can be adjusted according to actual conditions.
Preparation method：Sclerotin historical relic bonding reinforcement material is totally carried out in two steps preparation, and the first step first prepares liquid phase component,
It is made of toughening bonding agent B, accelerant C and distilled water, and in addition solid phase components are curing agent A, and second step is by above-mentioned liquid phase group
Divide and solid phase components are uniformly mixed in the ratio of accounting.Concrete operations are as follows：
Quantitative accelerant C is first dissolved in a small amount of water, quantitative toughening bonding agent B is dissolved in a small amount of water, after the two mixing again
The quantitative values for adding water to water are mended, this is liquid phase component.Take 2~3 additions of quantitative curing agent A (solid phase components) point above-mentioned before use
Liquid phase component stirs, and carries out historical relic repairing immediately and reinforces operation.The timing since being added in liquid phase component for the first time,
Operation need to be completed before the presetting period.Setting time according to the dosage of accelerant C change and change, and can be needed according to reparation into
Row adjustment.
Wherein curing agent is solid phase components, and toughening bonding agent, accelerating agent and water mixing form liquid phase component.Solid phase components and
Liquid phase component, which mixes to mix thoroughly in proportion, is made composition of the present invention.Solid phase components and liquid phase component are protected in sealing respectively
It can be stored more than three months or more in the case of depositing, but when the two is mixed and made into sclerotin historical relic bonding reinforcement material must be current existing
Match, and complete to repair before initial set and operate.
It is specific as follows in the reaction mechanism for the adhesive composition for sclerotin historical relic reparation for preparing the present invention above:
Fundamental reaction is the hydrolysis of synthos in the liquid phase, according to kinetics principle, such as single use
A kind of synthos all can be surrounded and be hindered the further progress of aquation due to the product that it is generated in hydrolytic process, and may
A large amount of impurity are introduced in aquation final product.Therefore, in actual use, it is typically to select two distinct types of calcium phosphate
Salt：A kind of hydrolysis is in acidity；A kind of hydrolysis is in alkalinity.Hydrolysis is made to occur together with acid-base neutralization reaction in this way, was both neutralized
The by-product that hydrolysis generates, and stabilize the pH value of entire aquation system, discuss that more systems has phosphoric acid at present
Four calcium/calcium monohydrogen phosphate system (TetCP/DCPA), tricalcium phosphate/calcium monohydrogen phosphate system (TCP/DCPA) etc..With TetCP/DCPA
Its reaction equation is as follows for system：
3Ca4(PO4)2O+3H2O—>2Ca5(PO4)3OH+2Ca2++4OH-
5CaHPO4+H2O—>Ca5(PO4)3OH+2H3PO4
H3PO4—>H++H2PO4 -
H2PO4 -—>H++HPO4 2-
HPO4 2-—>H++PO4 3-
H++OH-—>H2O
5Ca2++3PO4 3-+OH-—>Ca5(PO4)3OH
It reacts solidification after being mixed with liquid phase, whisker shape hydroxyapatite (HA) is ultimately formed, to sclerotin historical relic
There are bonding, reinforcement effect.
Specific embodiment presented below is illustrating technical scheme of the present invention.
Embodiment 1
(1) calcium phosphate dibasic anhydrous (DCPA)
Calcium phosphate dibasic dihydrate (DCPD) is placed in mortar manual fine grinding, by powder by 180 mesh standard sieves, is placed in electricity
120 DEG C of dehydration 12h, are fitted into agate spherical tank after cooling by medium of absolute ethyl alcohol, in horizontal planetary ball in hot blast drying box
Grinding about 8h in grinding machine, again drying obtain calcium phosphate dibasic anhydrous (DCPA) powder (granularity is less than 10 μm), and pack sealing is spare.
(2) tetracalcium phosphate：Tetracalcium phosphate (TTCP) is placed in mortar quick ground 180 mesh sieve, by ground powder
End using absolute ethyl alcohol as medium, ground in horizontal planetary ball mill about for 24 hours after, drying obtain ultra-fine tetracalcium phosphate powder (grain
Degree is less than 10 μm), pack sealing is spare.
(3) calcium hydroxy phosphate (HA), nanoscale (are less than 50nm), self-control or purchased in market.
(4) preparation of synthos curing agent
Weigh the calcium phosphate dibasic anhydrous of above-mentioned preparation respectively by quality proportioning 70.73%TTCP+26.27%DCPA+3%HA
(DCPA), tetracalcium phosphate (TTCP) and di calcium powder, are fitted into agate spherical tank, and using absolute ethyl alcohol as medium, ball milling mixes
12h is closed, takes out 80 DEG C of drying in an oven, obtains curing agent A, pack sealing is spare.
(5) prepared by toughening bonding agent：40% silicone-acrylic water-soluble lotion, other concentration are purchased in market.
(6) prepared by phosphate accelerating agent：44.76g Na are weighed respectively2HPO4·12H2O and 19.50g NaH2PO4·2H2O
It is uniformly mixed.
(7) preparation of the adhesive composition of bone repair：By 3 grams of accelerant Cs, 27 grams of distillation water dissolutions, 10 are added
Gram 40% silicone-acrylic water-soluble lotion is uniformly mixed, this is liquid phase component.100 grams of curing agent A is weighed in stainless steel circular bottom pot,
In the case of stirring, divide 2~3 addition liquid phase components, the so-called bonding strengthening agent of the present invention is obtained after mixing.It is effectively formed
It is as follows：
1 example of table, 1 product main performance (25 DEG C)
The repairing bonding operation of sclerotin historical relic is completed before the presetting period, curing is placed at room temperature and completes for 24 hours.Fig. 1 and Fig. 2
Respectively illustrate 3 days cured products of the present embodiment 1 compared with hydroxyapatite XRD spectrum with 3 days cured product microscopic appearances
(5000 times).
Embodiment 2
(1) curing agent A is prepared respectively by example 1 (1)~(6) step, there is toughening bonding agent B and accelerant C.
(2) prepared by sclerotin historical relic bonding reinforcement material：By 4 grams of accelerant Cs, 16 grams of dissolvings of distilled water, 20 grams are added
40% silicone-acrylic water-soluble lotion is uniformly mixed.100 grams of curing agent A is taken to divide 2~3 in the case of stirring in stainless steel circular bottom pot
It is secondary to add in above-mentioned mixed solution, the so-called bonding strengthening agent of the present invention is obtained after mixing.Effectively composition is as follows for it：
2 product main performance of Fig. 2 examples (25 DEG C)
The repairing bonding operation of sclerotin historical relic is completed before the presetting period, curing is placed at room temperature and completes for 24 hours.Fig. 3 and Fig. 4
Respectively illustrate 3 days cured products of the present embodiment 2 compared with hydroxyapatite XRD spectrum with 3 days cured product microscopic appearances
(5000 times).
Embodiment 3
(1) curing agent A, toughening bonding agent B and accelerant C are prepared respectively by example 1 (1)~(6) step.
(2) prepared by sclerotin historical relic bonding reinforcement material：By 2 grams of accelerant Cs, 23 grams of dissolvings of distilled water, 15 grams are added
40% silicone-acrylic water-soluble lotion is uniformly mixed.100 grams of curing agent A is taken to divide 2~3 in the case of stirring in stainless steel circular bottom pot
It is secondary to add in above-mentioned mixed solution, the so-called bonding strengthening agent of the present invention is obtained after mixing.Effectively composition is as follows for it：
3 product main performance of Fig. 3 examples (25 DEG C)
The repairing bonding operation of sclerotin historical relic is completed before the presetting period, curing is placed at room temperature and completes for 24 hours.Fig. 5 and Fig. 6
Respectively illustrate 3 days cured products of the present embodiment 2 compared with hydroxyapatite XRD spectrum with 3 days cured product microscopic appearances
(5000 times).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement and improvement for being made etc. should be included in the guarantor of the present invention
Within the scope of shield.
Claims (8)
1. a kind of adhesive composition for sclerotin historical relic reparation, which is characterized in that including mix when in use component A,
Component B, component C and water, the component A are synthos curing agent, and the component B is toughening binding agent, and the component C is phosphorus
Hydrochlorate accelerating agent；Wherein, when preparing the adhesive composition, the proportioning of each component is as follows in parts by weight：
2. as described in claim 1 be used for sclerotin historical relic reparation adhesive composition, which is characterized in that the component A by
Two or more synthos mix, and hybrid mode is using alcohol as medium, and it is small that fineness is milled in planetary mills
In 10 μm, then dry.
3. it to be used for the adhesive composition of sclerotin historical relic reparation as claimed in claim 2, which is characterized in that the synthos
For tricalcium phosphate, tetracalcium phosphate, calcium dihydrogen phosphate, calcium phosphate dibasic anhydrous or calcium hydroxy phosphate.
4. it to be used for the adhesive composition of sclerotin historical relic reparation as claimed in claim 2, which is characterized in that the alcohol is anhydrous
Ethyl alcohol.
5. it to be used for the adhesive composition of sclerotin historical relic reparation as described in claim 1, which is characterized in that the component B choosings
From：Collagen, gelatin, fluorocarbon resin, polyvinyl alcohol, acrylic resin, fibroin albumen, chitosan, polylactic acid, serine,
Polyethylene glycol, polyacrylamide, fluorine carbon emulsion, silicone acrylic emulsion, polyvinyl butyral, polyvinyl alcohol, carboxymethyl cellulose or
One or more in hydroxypropyl methyl cellulose mix, and the use of solvent are distilled water during mixing.
6. as described in claim 1 be used for sclerotin historical relic reparation adhesive composition, which is characterized in that the component C by
Two or more phosphate mixes, and mixed solvent is distilled water.
7. it to be used for the adhesive composition of sclerotin historical relic reparation as claimed in claim 6, which is characterized in that the phosphate is
Sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate.
8. it to be used for the adhesive composition of sclerotin historical relic reparation as described in claim 1, which is characterized in that the adhesive combines
Object is made by following steps：
Step 1, liquid phase component is prepared, liquid solution is made by solvent of distilled water respectively in component B and component C；
Step 2, component A, component B and component C are mixed according to weight.
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| CN202311343720.3A CN117402560A (en) | 2017-12-15 | 2017-12-15 | Adhesive composition for repairing bone relics and preparation method thereof |
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| CN109266285A (en) * | 2018-09-06 | 2019-01-25 | 顶立新材料科技有限公司 | A kind of environment-friendly water-based adhesive of multi-layered board gluing processing of lac modified polyvinyl acetate |
| CN110003848A (en) * | 2019-04-24 | 2019-07-12 | 李亚军 | A kind of preparation method of the modified legumin adhesive of no aldehyde |
| CN110668842A (en) * | 2019-10-28 | 2020-01-10 | 西北大学 | Reinforcing treatment method for porous bone and horn cultural relics |
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