CN103276627A - Multifunctional nano compound treating fluid for protecting paper cultural relics and preparation method thereof - Google Patents
Multifunctional nano compound treating fluid for protecting paper cultural relics and preparation method thereof Download PDFInfo
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- CN103276627A CN103276627A CN2013102082321A CN201310208232A CN103276627A CN 103276627 A CN103276627 A CN 103276627A CN 2013102082321 A CN2013102082321 A CN 2013102082321A CN 201310208232 A CN201310208232 A CN 201310208232A CN 103276627 A CN103276627 A CN 103276627A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012530 fluid Substances 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 22
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 22
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 22
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002105 nanoparticle Substances 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003672 processing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses multifunctional nano compound treating fluid for protecting paper cultural relics. The multifunctional nano compound treating fluid takes deionized water as a solvent, and comprises nano magnesium hydroxide, nano titanium dioxide and hydroxyethyl cellulose, wherein nano magnesium hydroxide accounts for 0.2-1.0% of the weight of deionized water, nano titanium dioxide accounts for 0.1-0.8% of the weight of deionized water, and hydroxyethyl cellulose accounts for 0.2-0.8% of the weight of deionized water. The invention also discloses a preparation method of the multifunctional nano compound treating fluid. The multifunctional nano compound treating fluid can be used for large-area treatment of the paper cultural relics, and can be used for providing protection for deacidification, solidification, light-resistant degradation and mould proofing of the paper cultural relics during a large-area treatment of the paper cultural relics. The pH value of the paper cultural relics treated by the multifunctional nano compound treating fluid can reach an alkalescence degree, and the paper cultural relics have a certain alkali residue, can resist external acid, can be greatly improved in tensile strength, and have a certain antibacterial property.
Description
Technical field
The present invention relates to a kind of papery historical relic treatment fluid, particularly a kind of multifunctional nano Combined Processing liquid that can be used for large-area treatment papery historical relic and preparation method thereof.
Background technology
The papery historical relic nowadays is among the grievous injury of acidifying, oxidation, biological corrosion and light-initiated degraded as the important media of record and succession human culture.The papery historical relic generally is material with the paper, and as time goes by, it is just suffering irreversible infringement.At this situation, various countries' books and historical relic management work person have taked a series of action.At present, existing many large tracts of land depickling processing methods that are used for papery historical relic depickling protection, the some of them method is no lack of commercialization.For some disputes that existing some depickling processing methods exist, main concentrate for current processing method the depickling of papery historical relic is handled and residual certain alkali in can not give the papery historical relic other performance, as mechanical strength, bacteriostasis property etc.Therefore studying a kind for the treatment of fluid efficient and can give the multi-faceted protection of papery historical relic in disposable large-area treatment papery historical relic has very important significance.
This project is subjected to country's culture science and technology to promote programme support.
Summary of the invention
Technical problem to be solved by this invention is, a kind of multifunctional nano Combined Processing liquid that can be used for multi-faceted protection papery historical relic is provided.
The technical problem that the present invention also will solve provides the preparation method of above-mentioned Combined Processing liquid.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of multifunctional nano Combined Processing liquid for the papery historical relic's protection; it is solvent with the deionized water; also comprise nano-sized magnesium hydroxide, nano titanium oxide and hydroxyethylcellulose; wherein; nano-sized magnesium hydroxide 0.2～1.0% of the ionized water weight that accounts for; nano titanium oxide 0.1～0.8% of the ionized water weight that accounts for, hydroxyethylcellulose 0.2～0.8% of the ionized water weight that accounts for.
Wherein, described nano-sized magnesium hydroxide particle diameter is 20～50nm, Unimodal Distribution.
Wherein, described nano titanium oxide is anatase titanium dioxide, and particle diameter is 10～50nm.
Wherein, described hydroxyethylcellulose molecular weight is 1～50,000.
Multifunctional nano Combined Processing liquid for the papery historical relic's protection of the present invention is the depickling material with the nano-sized magnesium hydroxide, is anti-light degradation and mildew-resistant material with nano titanium oxide, with the hydroxyethylcellulose is to reinforce material.This treatment fluid is with immersion way large-area treatment papery historical relic, makes the papery historical relic after the processing have the characteristic of light aging resisting and heat ageing, and can preserve for a long time.Be the depickling material with the nano-substance, it is fast to have depickling speed, and processing method is easy, economical, to the papery historical relic permeate, advantage such as side effect is little; Adopt hydroxyethylcellulose and papery historical relic to have extraordinary compatibility, can reach the purpose that increases substantially papery historical relic tensile strength.
The preparation method of above-mentioned multifunctional nano Combined Processing liquid for the papery historical relic's protection, this method may further comprise the steps:
(1) nano-sized magnesium hydroxide of getting formula ratio is scattered in the deionized water of 1/2 formula ratio, and in disperseing with stirring under the synergy ultrasonic under 25～90 ℃, jitter time is 1～2h;
(2) hydroxyethylcellulose of getting formula ratio slowly is dissolved in the deionized water of 1/2 formula ratio, under 25～90 ℃, stirs 4～14h;
(3) nano titanium oxide of getting formula ratio adds in the mixture that step (2) obtains, in disperseing jitter time 1～2h ultrasonic with stirring under the synergy under 25～90 ℃;
(4) mixture of the acquisition that step (3) is obtained, in being dispersed under the synergy in the mixture that step (1) obtains with stirring ultrasonic under 25～90 ℃, jitter time is 3～5h, obtains multifunctional nano Combined Processing liquid.
Wherein, stir speed (S.S.) is 100～800rpm, preferred 200～400rpm; Ultrasonic power is 20～80KHz, preferred 30～50KHz, 0.3W/cm
2
Beneficial effect: in the technical scheme of the present invention, be main active ingredient with nano-substance, can be under the situation of MIN change papery historical relic outward appearance, little to the side effect of papery historical relic, the efficient height, method of operating is simple, and is economical reliable and can be disposable reach depickling, reinforcing, mildew-resistant and anti-photodegradative purpose processing papery historical relic the time.Be the depickling material with the little nano-sized magnesium hydroxide of dispersed nano particle diameter, can be effectively in and the acid in the papery historical relic, and residual certain alkali makes it resist the erosion of external acid.Adopted the composition of nanometer anatase titania as Combined Processing liquid, can resist to a certain extent light to the cellulosic infringement of papery historical relic and suppress fungi and mould to the infringement of papery historical relic.With with papery historical relic compatibility preferably hydroxyethylcellulose remedied the papery historical relic and handled the defective that back intensity reduces through aqueous treating fluid, and can increase the tensile strength of papery historical relic to a certain extent as the strengthening agent of this treatment fluid.With water as carrier, its deacidification efficiency height, and nano particle is uniformly dispersed.Therefore, described treatment fluid can make the papery historical relic can resist multiple external infringement in disposable processing procedure in large-area treatment papery historical relic when remedying the aqueous treating fluid defective.
The specific embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Used nano-sized magnesium hydroxide particle diameter is 20～50nm in following examples, Unimodal Distribution; Nano titanium oxide is anatase titanium dioxide, and particle size is 10～50nm, and the hydroxyethylcellulose molecular weight is 1～50,000.
Used pattern is for obviously taking a sample the paper of acidifying from the Republic of China period according to ISO 7213 among the embodiment, and Substance is 66.67g/m
2, pattern is cut into respectively and is of a size of 1.5 * 18cm, 3.0 * 3.0cm and 2.4cm diameter and is used for subsequent treatment.For making measurement result more reliably reach standardization, all samples all is placed on the 24h that outgases in 50 ℃, appropriate vacuum condition.To deposit in room temperature, relative humidity be to carry out follow-up test after the 16h at least in 35% the environment to pattern subsequently.
Embodiment 1:
A kind of multifunctional nano Combined Processing liquid for the papery historical relic's protection; it is solvent with the deionized water; also comprise nano-sized magnesium hydroxide, nano titanium oxide and hydroxyethylcellulose; wherein; nano-sized magnesium hydroxide 0.2% of the ionized water weight that accounts for; nano titanium oxide 0.1% of the ionized water weight that accounts for, hydroxyethylcellulose 0.4% of the ionized water weight that accounts for.
The preparation method is as follows:
(1) under the room temperature, take by weighing the 0.4g magnesium hydroxide and add under ultrasonic agitation and mechanical agitation in the 100g deionized water, mechanical agitation speed is 200rpm, and supersonic frequency is 40KHz, and mixing time is 1h.
(2) the 0.8g hydroxyethylcellulose slowly is dissolved in the 100g deionized water, stirs 6h under the room temperature.
(3) get the 0.2g nano titanium oxide and add down in the step (2) in the fully decentralized hydroxyethylcellulose in mechanical agitation and ultrasonic agitation are collaborative, operating temperature is room temperature.Mechanical agitation speed is 200rpm, and supersonic frequency is 40KHz, and mixing time is 1.5h.
(4) step (3) is obtained mixture, under ultrasonic and stirring synergy, being dispersed in step (1) the nano-sized magnesium hydroxide aqueous solution under the room temperature, obtain final multifunctional nano Combined Processing liquid.Wherein jitter time is 4h.
The pattern that is cut into the various sizes shape is soaked in this multifunctional nano Combined Processing liquid behind the 20min, takes out air-dry.Subsequently each pattern is positioned over 24h in 23 ℃, the environment of relative humidity 50%, treats that follow-up pH value, alkali are residual, mechanical performance, aberration, light transmittance, whiteness and anti-microbial property test.Paper before and after handling is carried out light aging and its endurance quality of thermal ageing test.
Test result shows that pH value of paper after treatment has greatly improved, and is promoted to 8.4 by 3.5; Tensile strength also is promoted to 900N/m by 700N/m; It is residual that paper has certain alkali, is worth for 3.103%vs.Mg (OH)
2Have certain bacteriostasis property through this nano combined treatment fluid sheet processed, antibacterial circle diameter is 34.62mm; Ultraviolet-visible photometer and whiteness test all show through this nano combined treatment fluid sheet processed can absorb certain ultraviolet ray, stops light that the degraded of paper fibre element is destroyed; The CIE color coordinates shows, through the slight Δ E of this nano combined treatment fluid sheet processed change color
*=0.77, meet the papery historical relic's protection requirement of " restoring the old as the old keeps original appearance "; Accelerate heat ageing and light aging test and all show through the nano composite material sheet processed to have good stable, can preserve for a long time.
Embodiment 2:
A kind of multifunctional nano Combined Processing liquid for the papery historical relic's protection; it is solvent with the deionized water; also comprise nano-sized magnesium hydroxide, nano titanium oxide and hydroxyethylcellulose; wherein; nano-sized magnesium hydroxide 1.0% of the ionized water weight that accounts for; nano titanium oxide 0.8% of the ionized water weight that accounts for, hydroxyethylcellulose 0.2% of the ionized water weight that accounts for.
Embodiment 3:
A kind of multifunctional nano Combined Processing liquid for the papery historical relic's protection; it is solvent with the deionized water; also comprise nano-sized magnesium hydroxide, nano titanium oxide and hydroxyethylcellulose; wherein; nano-sized magnesium hydroxide 0.4% of the ionized water weight that accounts for; nano titanium oxide 0.6% of the ionized water weight that accounts for, hydroxyethylcellulose 0.8% of the ionized water weight that accounts for.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. multifunctional nano Combined Processing liquid that is used for the papery historical relic's protection; it is characterized in that; it is solvent with the deionized water; also comprise nano-sized magnesium hydroxide, nano titanium oxide and hydroxyethylcellulose; wherein; nano-sized magnesium hydroxide 0.2～1.0% of the ionized water weight that accounts for, nano titanium oxide 0.1～0.8% of the ionized water weight that accounts for, hydroxyethylcellulose 0.2～0.8% of the ionized water weight that accounts for.
2. the multifunctional nano Combined Processing liquid for the papery historical relic's protection according to claim 1 is characterized in that described nano-sized magnesium hydroxide particle diameter is 20～50nm.
3. the multifunctional nano Combined Processing liquid for the papery historical relic's protection according to claim 1 is characterized in that described nano titanium oxide is anatase titanium dioxide, and particle diameter is 10～50nm.
4. the multifunctional nano Combined Processing liquid for the papery historical relic's protection according to claim 1 is characterized in that described hydroxyethylcellulose molecular weight is 1～50,000.
5. the preparation method of the described multifunctional nano Combined Processing liquid for the papery historical relic's protection of claim 1 is characterized in that this method may further comprise the steps:
(1) nano-sized magnesium hydroxide of getting formula ratio is scattered in the deionized water of 1/2 formula ratio, and in disperseing with stirring under the synergy ultrasonic under 25～90 ℃, jitter time is 1～2h;
(2) hydroxyethylcellulose of getting formula ratio slowly is dissolved in the deionized water of 1/2 formula ratio, under 25～90 ℃, stirs 4～14h;
(3) nano titanium oxide of getting formula ratio adds in the mixture that step (2) obtains, in disperseing jitter time 1～2h ultrasonic with stirring under the synergy under 25～90 ℃;
(4) mixture of the acquisition that step (3) is obtained, in being dispersed under the synergy in the mixture that step (1) obtains with stirring ultrasonic under 25～90 ℃, jitter time is 3～5h, obtains multifunctional nano Combined Processing liquid.
6. the preparation method of the multifunctional nano Combined Processing liquid for the papery historical relic's protection according to claim 5 is characterized in that stir speed (S.S.) is 100～800rpm, and ultrasonic power is 20～80KHz, 0.3W/cm
2
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532669A (en) * | 2014-12-05 | 2015-04-22 | 鲁继烈 | Water-tolerant light-resistant ozone-proof composition for protection of character image and cultural relics |
| CN104652173A (en) * | 2015-02-04 | 2015-05-27 | 江志鑫 | Book treatment method |
| CN104652172A (en) * | 2015-02-04 | 2015-05-27 | 广州乾程化工科技发展有限公司 | Paper historical relic deacidifying and reinforcing protective material and preparation method thereof |
| CN105088870A (en) * | 2015-07-15 | 2015-11-25 | 国家图书馆 | A paper deacidification agent and its paper deacidification system and method |
| CN105885547A (en) * | 2016-06-14 | 2016-08-24 | 陕西师范大学 | Deacidifying and strengthening agent for cellulose acetate film |
| CN106592325A (en) * | 2016-11-24 | 2017-04-26 | 陕西科技大学 | Multifunctional protective liquid for paper-based material printed matters and application |
| CN106758514A (en) * | 2016-12-15 | 2017-05-31 | 陕西师范大学 | A kind of method that archives of paper quality reinforces depickling |
| CN107142787A (en) * | 2017-05-24 | 2017-09-08 | 常德金德镭射科技股份有限公司 | A kind of preparation method of mould proof coating paper |
| CN107287984A (en) * | 2017-08-07 | 2017-10-24 | 陕西师范大学 | A kind of cultural artifact surface white lead returns lead and removes liquid |
| CN107326742A (en) * | 2017-07-23 | 2017-11-07 | 复旦大学 | A kind of depickling of paper fibre and reinforcement guard method |
| CN108004846A (en) * | 2017-11-28 | 2018-05-08 | 华南理工大学 | A kind of new ancient books enhancing reinforcement means |
| CN108221464A (en) * | 2018-03-27 | 2018-06-29 | 郑州博物馆 | A double-layer reinforcement solution for the protection of paper cultural relics |
| CN108221482A (en) * | 2018-01-29 | 2018-06-29 | 郑州博物馆 | A reinforcement solution for the protection of paper cultural relics |
| CN108360296A (en) * | 2018-03-06 | 2018-08-03 | 杭州众材科技有限公司 | A kind of paper sheet deacidification agent and its preparation method and application |
| CN109518527A (en) * | 2018-10-10 | 2019-03-26 | 华南理工大学 | A kind of multi-functional ancient books repairs liquid and its processing method |
| CN109695182A (en) * | 2019-01-24 | 2019-04-30 | 华南理工大学 | A kind of method depickling enhancing treatment fluid and aging paper is handled |
| CN110424185A (en) * | 2019-08-06 | 2019-11-08 | 复旦大学 | Fragility fears the paper pulp composite repair method of water paper relics and repairs paper pulp |
| CN111270559A (en) * | 2019-09-09 | 2020-06-12 | 华南理工大学 | Nano-cellulose/nano-zinc oxide multifunctional protective solution, preparation method thereof and method for protecting paper documents |
| CN114411446A (en) * | 2022-02-17 | 2022-04-29 | 复旦大学 | Deacidifying, reinforcing and antibacterial composite functional protective agent and preparation method and application thereof |
| CN115558396A (en) * | 2022-11-08 | 2023-01-03 | 陕西师范大学 | A kind of cellulose acetate film deacidification strengthening agent and its preparation method and application |
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| CN111270559A (en) * | 2019-09-09 | 2020-06-12 | 华南理工大学 | Nano-cellulose/nano-zinc oxide multifunctional protective solution, preparation method thereof and method for protecting paper documents |
| CN114411446A (en) * | 2022-02-17 | 2022-04-29 | 复旦大学 | Deacidifying, reinforcing and antibacterial composite functional protective agent and preparation method and application thereof |
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Application publication date: 20130904 |