WO2019105168A1 - 一种新型的古籍脱酸修复方法 - Google Patents

一种新型的古籍脱酸修复方法 Download PDF

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Publication number
WO2019105168A1
WO2019105168A1 PCT/CN2018/113229 CN2018113229W WO2019105168A1 WO 2019105168 A1 WO2019105168 A1 WO 2019105168A1 CN 2018113229 W CN2018113229 W CN 2018113229W WO 2019105168 A1 WO2019105168 A1 WO 2019105168A1
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Prior art keywords
deacidification
ancient
solution
ancient books
alkaline
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PCT/CN2018/113229
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English (en)
French (fr)
Inventor
樊慧明
陈建华
王海滨
甘谦
李嘉禾
高达
郭鸣凤
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华南理工大学
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Priority to EP18883588.8A priority Critical patent/EP3643834A4/en
Publication of WO2019105168A1 publication Critical patent/WO2019105168A1/zh

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the invention relates to the field of deacidification repair of ancient books, and particularly relates to a novel method for deacidification repair of ancient books.
  • the existing deacidification repair processes mainly include liquid phase deacidification and gas phase deacidification.
  • the principle is to neutralize the acid in the ancient books with an alkaline deacidification agent to achieve the purpose of deacidification and repair.
  • the liquid phase deacidification repair method is mainly divided into organic solution deacidification and aqueous acid deacidification;
  • organic solvent deacidification repair method The main methods of organic solvent deacidification repair method are Wet method, FMC method, barium hydroxide -
  • the methanol solution is deacidified and repaired, and the organic solution deacidification repair method has the advantages of high deacidification recovery efficiency, simple operation and low cost.
  • organic solvent methods are flammable and some organic solvents are highly toxic. Most of them are not suitable for oil-soluble ink prints, which will cause ancient inks to melt and deface ancient books. Too much toxicity is very demanding on the safety of the operation.
  • the aqueous acid deacidification method has the advantages of environmental safety, easy operation, economy, and good acid-removing and repairing effect.
  • there are also phenomena such as deformation and shrinkage of the processed paper literature, which have an impact on certain writing, and thus Conducive to large-scale deacidification repair.
  • the aqueous solution method there is no solution to the deacidification treatment of the whole book by the aqueous solution method. If the whole ancient book is directly deacidified and repaired, the paper will stick to each other, causing serious secondary damage.
  • the ancient books should be dismantled into a single page for processing. After the paper documents are processed, they are re-stitched. The ancient books have been placed for a long time, and the strength is very low.
  • the gas phase deacidification repair method is mainly divided into a diethylzinc method and a morpholine deacidification method.
  • Diethylzinc deacidification method When diethylzinc meets with acidic hydrogen ions in ancient books, it not only reacts with hydrogen ions in paper, but also rapidly neutralizes hydrogen in water to form solid zinc oxide. This solid zinc oxide remains on the surface of the paper and can have a certain deacidification repair effect. However, diethylzinc spontaneously ignites when exposed to air, which is a great danger. The paper literature is most afraid of fire, and zinc oxide. The residue will also partially accelerate the photooxidation of the paper fibers, making the paper yellow and aging, so this method is not very good.
  • Morpholine deacidification method Under normal conditions, morpholine is a liquid, and under vacuum conditions, it can be mixed with water to become a gas, and can react with hydrogen ions in ancient books to achieve the purpose of deacidification repair. This method is easy to change the color of the paper, making the news paper, journals, etc. yellow, the process can not be used to strengthen, and the investment in equipment and instruments is large, and large-scale promotion is limited. From the application of foreign acid-removing technology, in the 1970s and 1980s, the advantages of gas-phase deacidification repair in large-scale treatment were highly praised by people, but the process conditions were high, there were safety hazards, and the toxicity was large and the investment was large. The disadvantage of uneven processing effect limits its wide application.
  • the present invention provides a novel method for deacidification of ancient books.
  • the invention combines a gas phase deacidification repair process and a liquid phase deacidification repair process, using a gas phase / a liquid phase and a gas phase /
  • the solid phase deacidification repair process not only avoids the secondary damage of paper adhesion caused by liquid phase deacidification repair, but also the process is not to destroy the original temperature and humidity of ancient books, and does not need to dry the ancient books, the fiber is not It will age and break, and the ancient books will not be yellow and damaged.
  • a new type of ancient acid deacidification repair method firstly, the ancient books to be treated are put into a closed deacidification repairing device, and after sealing, the system is subjected to dehumidification operation and vacuuming operation to keep the system dry and under negative pressure. After being stable, turn it on Fan group
  • the deacidification agent is directly sent to the deacidification repairing device through the gas pipeline, or the alkaline deacidification solution is atomized by the ultrasonic atomizer, and then the atomized alkaline deacidification solution is sent to the gas pipeline through the gas pipeline.
  • the ancient books to be treated are sufficiently uniformly absorbed by the alkaline deacidification agent, and at the same time, the ancient books are pH monitoring to achieve deacidification repair of ancient books;
  • the ancient books include dealing with ancient acid books, archives, literature materials, books, newspapers, papers, calligraphy, cotton and linen.
  • the humidifying operation is to draw the humidity in the system to 10% ⁇ 90% through the dehumidifier, and maintain the 2 ⁇ 24 Hours, turn off the dehumidifier after reaching the target time.
  • the dehumidification operation time depends on the original humidity of the ancient books and the volume of the sealing device. When the original humidity of the ancient books is 8% ⁇ 9%, the volume of the device is the total volume of the ancient books to be processed 1.5 ⁇ 2. When doubled, dehumidification is 2 ⁇ 24h; when the original humidity is reduced by 10%, the dehumidification time is reduced by 2 ⁇ 6h; when the volume of the device is doubled, the dehumidification time is increased by 3 ⁇ 8h.
  • the vacuuming operation is performed after the dehumidification operation is completed, and the pressure in the system is drawn to 0 by a vacuum pump. -0.08mpa, the vacuum pump is turned off after the target pressure is reached, and the closed system maintains a stable negative pressure state until the deacidification operation is completed.
  • the ultrasonic atomizer is an ultrasonic transducer, and the ultrasonic transducer is placed in a container equipped with a deacidifying agent, and the power is turned on, and the deacidification structure is obtained by high frequency resonance of the piezoelectric ceramic.
  • the deacidification agent is a nano-sized alkaline deacidification powder material, an alkaline organic solution or an alkaline inorganic solution; the pH value can be maintained stable for a long time, no toxicity, and the pH value is 7-13.
  • the deacidification agent includes but is not limited to NaOH solution, Ca(OH) 2 solution, Cu(OH) 2 solution, Fe(OH) 3 solution, KOH solution, Na 2 CO 3 solution, NaHCO 3 solution, NH 3 ⁇ H 2 O solution, ethylenediamine solution, phosphate solution, borate solution and other alkaline materials; solution is dispersed into micron to nanometer droplets by pressure or ultrasonic atomizer, the average particle size is 1nm ⁇ 2 ⁇ m Between and through the gas pipeline connected to the closed deacidification device.
  • the deacidifying agent includes, but is not limited to, nano NaOH powder, Ca(OH) 2 powder, Cu(OH) 2 powder, Fe(OH) 3 powder, KOH powder, Na 2 CO 3 All alkaline powder materials such as powder or NaHCO 3 powder, ethylenediamine powder.
  • the blasting system is to slowly introduce the nano-scale alkaline deacidified powder material or the ultrasonic deoxidizer atomized deacidification agent into the closed deacidification repairing device through the gas pipeline, and let the system The deacidification agent circulates and is evenly distributed.
  • the air humidity in the control system is maintained at 10% to 90%.
  • the acid-removing repair device has an ancient country pH monitoring, and the pH of the monitored ancient books reaches about 7 to 8.5 and is maintained. After 1 ⁇ 48 hours, turn off the system.
  • the length of time depends on the acidification degree of the ancient books and the volume of the sealing device.
  • the volume of the device is the total volume of the ancient books to be processed 1.5 ⁇ 2.
  • the acid removal is maintained for 2 ⁇ 5 hours; for every 0.2 increase of the original pH, the deacidification maintenance time is reduced by 1 ⁇ 6h; for every doubling of the volume of the device, the deacidification maintenance time is increased by 3 ⁇ 8h.
  • Figure 1 is a schematic view showing the structure of the deacidification repairing device of the present invention
  • Figure 3 is a schematic structural view of a bookshelf
  • Figure 4 is a gas flow diagram of the present invention.
  • the structure of the deacidification repairing device of the present invention is as follows, as shown in Fig. 1 to Fig. 4, the deacidification repairing device , including double open front door 1, fan set 4, dehumidifier 6, vacuum pump 7, lamp 10, intermediate partition 11, gas pipe small hole 12, back plate 13, ultrasonic atomizer 14, gas pipe 15 and pulley track 18;
  • One side of the device is provided with a double open front door 1;
  • the intermediate partition 11 divides the device into an upper layer and a lower layer, and the bottom surface of the upper layer and the lower layer are each provided with a fan group 4, and the back plate 13 of the device opposite to the device door
  • the outer surface is provided with a dehumidifier 6, a vacuum pump 7 and an ultrasonic atomizer 14;
  • a lamp 10 is fixed around the lower portion of the intermediate partition;
  • the gas pipe 15 is located at the upper layer of the intermediate partition 11 and the gas pipe is
  • a gas pipe orifice 12 is opened in the upper portion, and the gas pipe 15 is connected
  • a visible window 2 having two visible windows 2 on both sides of the front door 1 and on the left and right sides of the device. Also included are a hygrometer 5, a pressure gauge 8 and a pH meter 9; the hygrometer 5, the pressure gauge 8 and the pH meter 9 are all disposed inside the apparatus.
  • the double-open front door 1 is fixed with a PLC control system 16, which controls the fan group 4, the dehumidifier 6, the vacuum pump 7, the ultrasonic atomizer 14, the lamp 10 and the bookshelf 19 to be integrated, and monitors the hygrometer 5 and the pressure.
  • the device is composed of an outer layer material and an inner layer material, the outer layer material is carbon steel, and the inner layer material is stainless steel; the total width of the device is 1 m ⁇ 2.5 m, the height is 1 m ⁇ 2.5 m, and the length is 3 m ⁇ 12 m.
  • a water tank 3 and a drain valve 17 are provided; a bottom surface of the lower layer is provided with a water pool 3; the water tank 3 is located on both sides of the device and the floor of the backboard, and the height of the water tank 3 is 1 to 10 cm below the ground, and the width is 1 ⁇ 10cm; the water tank 3 is connected with the drain valve 17; the pulley track 13 has two paths, and the width between the two pulley tracks 13 is the same as the width of the bookshelf 19.
  • the intermediate partition 11 is provided with an air outlet 20, and the flow area is increased from the near and far direction of the fan group due to the faster flow velocity of the portion near the fan.
  • the bookshelf 19 is made of stainless steel and has rollers on the bottom; the bookshelf is provided with a stainless steel chain, the book basket is fixed on the chain, the chain is driven by the motor, and the book basket is moved up and down after the motor is turned on, so that the book absorbs the aerosol more uniformly;
  • the book basket is designed with a narrow width and a narrow width.
  • the side of the ancient book can be placed with the side turned upside down. The wind from the top to the bottom of the fan group 4 makes the ancient book slightly open, so that the deacidification agent penetrates more evenly.
  • the deacidification device takes the "medical ancient book" - People's Health Publishing House, 1937 edition, 5 copies of about 0.004m 3 , sampled and measured the original moisture of the paper in the book is about 8.6%, put the book into the 0.25m * 0.25m * 0.1m volume of 0.00625m 3
  • the system is first dehumidified, the dehumidification time is 4 h, and the dehumidifier is turned off after the arrival time. Then, the vacuum pump was turned on, and the pressure inside the system was pumped to -0.05 mpa, and then the vacuum pump was turned off.
  • the ultrasonic atomizer select the NaOH solid and water in a ratio of mass ratio of 20:80, put it into the container, use the ultrasonic transducer to atomize the prepared NaOH solution, and import it through the gas pipeline.
  • the deacidification repair operation is carried out in the sealed container.
  • the gas pipeline valve By controlling the gas pipeline valve, the air humidity in the system is controlled to be about 50%, and the pH value of the ancient books is monitored while neutralizing the acidic substances in the paper; when the pH of the monitored ancient books reaches 7.2, Continue to maintain the system stable for 2h, then shut down the system.
  • the deacidification device takes the "medical ancient book” - People's Health Publishing House, 1937 edition, 5 copies of about 0.004m 3 , sampled and measured the original moisture of the paper in the book is about 9.2%, put the book into the 0.25m * 0.25m * 0.1m volume of 0.00625m 3
  • the system is first dehumidified, the dehumidification time is 3 h, and the dehumidifier is turned off after the arrival time. Then open the vacuum pump and pump the pressure inside the system to -0.07mpa and then turn off the vacuum pump.
  • the ultrasonic atomizer select the NaOH solid and water in a ratio of mass ratio of 20:80, put it into the container, use the ultrasonic transducer to atomize the prepared NaOH solution, and import it through the gas pipeline.
  • the deacidification repair operation is carried out in the sealed container.
  • the gas pipeline valve By controlling the gas pipeline valve, the air humidity in the system is controlled to be about 50%, and the pH value of the ancient books is monitored while neutralizing the acidic substances in the paper; when the pH of the monitored ancient books reaches 7.2, Continue to maintain the system stable for 2h, then shut down the system.
  • the deacidification device takes the "medical ancient book" - People's Health Publishing House, 1937 edition, 5 copies of about 0.004m 3 , sampled and measured the original moisture of the paper in the book is about 7.3%, put the book into the 0.25m * 0.25m * 0.1m volume of 0.00625m 3
  • the system is first dehumidified, the dehumidification time is 4 h, and the dehumidifier is turned off after the arrival time. Then, the vacuum pump was turned on, and the pressure inside the system was pumped to -0.05 mpa, and then the vacuum pump was turned off.
  • the ultrasonic atomizer select the NaOH solid and water according to the mass ratio of 30:70, mix it into the container, use the ultrasonic transducer to atomize the prepared NaOH solution, and import it through the gas pipeline.
  • the deacidification repair operation is carried out in the sealed container.
  • the gas pipeline valve By controlling the gas pipeline valve, the air humidity in the system is controlled to be about 50%, and the pH value of the ancient books is monitored while neutralizing the acidic substances in the paper; when the pH of the monitored ancient books reaches 7.2, Continue to maintain the system stable for 2h, then shut down the system.

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  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

一种新型的古籍脱酸修复方法，该处理方法为：首先将待处理的古籍放入密闭脱酸修复装置中，密封好后先后对系统进行抽湿操作和抽真空操作，使体系维持干燥，并且在负压下保持稳定后，开启风扇组（4），通过气体管道（15）直接将纳米级碱性脱酸粉体送至脱酸修复装置中，或先通过超声雾化器（14）将碱性脱酸溶液雾化，然后再通过气体管道（15）送至脱酸修复装置中，使待处理的古籍充分均匀地吸收碱性脱酸剂，同时对古籍pH及湿度进行监测，实现对古籍的脱酸修复。

Description

一种新型的古籍脱酸修复方法 技术领域
本发明涉及古籍脱酸修复领域，具体涉及一种新型的古籍脱酸修复的方法。
背景技术
在中国各种各样的图书馆、博物馆、档案馆中，保存在成千上万的珍贵书籍、书画、现代报纸、档案和其他文物资料 , 它们是中华民族的优秀传统文化精华 , 具有重要的历史价值、文化价值、信息价值，是中华文化遗产中的重要组成部分，具有不可复制的历史意义。纸张，作为这些文字精华的载体，随着岁月的流逝，遭虫蛀、酸化、霉变、破损的情况越来越严重，情况岌岌可危。纸张由纤维原料抄造而成，纤维素的稳定性是维持古籍物理性能最重要的条件之一，纤维素在中性和弱碱性条件下是相对稳定的，一般不易被水解和氧化，但是在酸性条件下，由于酸的催化作用，纤维素的水解作用显著增强，纤维素水解后，由于聚合度降低，古籍的强度也随之降低，时间久了，古籍就会粉化。因为生产时的酸性化学品存留、老化降解产生的有机酸、使用存贮环境造成的酸化等多种因素均可能导致纸张的酸化加剧。因此，对纸质文献进行彻底的脱酸修复研究已经迫在眉睫。目前尽管国内外研究机构已经开展各种对纸质文献的脱酸修复研究，但是至今仍未获得能实际应用的成熟脱酸修复技术。
现有的脱酸修复工艺主要有液相脱酸和气相脱酸，其原理都是用碱性脱酸剂将古籍中的酸中和而达到脱酸修复目的。
液相脱酸修复法主要分为有机溶液脱酸和水溶液脱酸；
有机溶剂脱酸修复法主要方法有韦托法， FMC 法，氢氧化钡 - 甲醇溶液脱酸修复，有机溶液脱酸修复法具有脱酸修复效率高，操作简单，成本低等优点。目前日本、德国、意大利、美国等西方国家大多采用有机溶剂法，然而有机溶剂易燃、部分有机溶剂毒性强，大部分不适用于油溶性油墨印刷品，会造成古籍油墨溶化，污损古籍，而且毒性太强对操作的安全性要求很高。
水溶液脱酸修复法具有对环境安全、便于操作、经济、脱酸修复效果好的优点，但也存在着处理后的纸质文献出现变形、皱缩等现象，对某些字迹有影响，因而不利于规模化脱酸修复。目前国际上还没有解决水溶液法对整本图书进行脱酸修复处理的技术，如果直接对整本古籍进行脱酸修复处理，纸张之间会相互粘连，造成严重的二次破损，要处理都必须先要将古籍拆开成单页进行处理，纸质文献处理完成后再重新装订，古籍放置时间久了本来就强度很低，拆开非常容易造成破损，再把文献放到溶液中浸泡以后，纸张的强度就更低了，虽然能够脱酸修复，但是对古籍的二次损坏太严重，再者，书籍经过液体浸泡后需要烘干，烘干过程很容易造成纤维的加速老化，纤维断裂，使得纸张发黄，甚至破损，而且此方法处理过程繁杂，周期长，并不适用。
气相脱酸修复法主要分为二乙基锌法和吗啉脱酸法。
二乙基锌脱酸法：二乙基锌与古籍中的酸性氢离子相遇时，不仅能和纸中的氢离子发生反应，还能迅速中和水中的氢，生成固体的氧化锌。这种固体氧化锌留在纸的表面，可以有一定的脱酸修复效果，但是二乙基锌遇空气会自燃，存在很大的危险，纸质的文献最怕的就是火了，而且氧化锌的残留也会部分程度上加速纸张纤维的光氧化，使纸张发黄、老化，所以此方法也不太好。
吗啉脱酸法：正常情况下，吗啉是液体，而在真空条件下它能与水混合可变成气体，能与古籍中的氢离子发生反应达到脱酸修复目的。这种方法容易改变纸张颜色，使新闻纸、期刊等发黄，处理过程不能起到加固作用，而且加上设备、仪器投资很大，大规模推广受到限制。从国外脱酸修复技术的应用情况来看，七、八十年代，气相脱酸修复以其大批量处理的优点倍受人们的推崇，但工艺条件要求高，存在安全隐患，毒性大、投资大、处理效果不均匀的缺点限制了它的广泛应用。
目前国内外已存在很多种类似的气相和液相的脱酸修复工艺，但是都存在各自的缺陷，例如成本高，操作难度大，脱酸剂毒性大，不能大规模化，存在安全隐患，污染环境等，至今为止还没有发现一个能实际应用的古书脱酸修复方法。
发明内容
针对上述内容，为了克服上述问题或者至少部分的解决上述问题，本发明是提供一种新型的古籍脱酸修复方法。
本发明将气相脱酸修复工艺和液相脱酸修复工艺结合在一起，采用气相 / 液相和气相 / 固相脱酸修复工艺，既避免了液相脱酸修复会造成纸张粘连的二次损伤，而且本工艺旨在不破坏古籍原有的温度与湿度，不需要对古籍进行烘干操作，纤维不会老化断裂，古籍也不会发黄破损。同时也避免了气相脱酸修复找不到合适碱性气体脱酸剂的烦恼，大多数有机无机碱性液体和 纳米级碱性脱酸粉体材料 均可以使用本工艺对古籍进行脱酸修复操作。
一种新型的古籍脱酸修复方法，首先将待处理的古籍放入密闭脱酸修复装置中，密封好后先后对系统进行抽湿操作和抽真空操作，使体系维持干燥，并且在负压下保持稳定后，开启 风扇组 ，通过气体管道直接将脱酸剂送至脱酸修复装置中，或先通过超声雾化器将碱性脱酸溶液雾化，然后将雾化后的碱性脱酸溶液再通过气体管道送至脱酸修复装置中，使待处理的古籍充分均匀地吸收碱性脱酸剂，同时对古籍 pH 监测，实现对古籍的脱酸修复；
所述古籍包括处理古代酸性书本、档案、文献资料、图书、报刊、纸张、字画、棉和麻。
上述方法中，所述的密闭装置密封性好，体系保持室温，体系内可以达到较高的干度和较高的真空度，密封装置体积适合；所述装置体积与待处理的古籍总体积之间满足，装置体积：待处理的古籍总体积 =1.1:1~50:1 。
上述方法中，所述抽湿操作，是通过抽湿机将体系内的湿度抽到 10%~90% ，并维持 2~24 小时，达到目标时间后关闭抽湿机。抽湿操作时间取决于古籍的原始湿度和密封装置体积，当古籍原始湿度为 8%~9% 时，装置体积为待处理古籍总体积 1.5~2 倍时，抽湿 2~24h ；当原始湿度每减少 10% ，抽湿时间减少 2~6h ；当装置体积每增大一倍，抽湿时间增加 3~8h 。
上述方法中，所述抽真空操作，是在抽湿操作完成后再进行的，通过真空泵将体系内压力抽到 0 至 -0.08mpa ，达到目标压力后关闭真空泵，密闭体系维持稳定负压状态直至脱酸操作完成。
上述方法中，所述的超声雾化器为超声换能器，将超声换能器放入装有脱酸剂的容器中，接通电源，通过压电陶瓷高频谐振，将脱酸剂结构分散而雾化成小分子的气雾。
上述方法中，所述脱酸剂为纳米级碱性脱酸粉体材料、 碱性有机物溶液或碱性无机物溶液；pH值能在较长时间维持稳定，无毒性、pH值为7~13；所述脱酸剂包括但不仅限于 NaOH 溶液 ， Ca(OH)2 溶液 ， Cu(OH)2 溶液 ， Fe(OH)3 溶液 ， KOH 溶液 ， Na2CO3 溶液 ， NaHCO3 溶液 ， NH3·H2O 溶液，乙二胺溶液，磷酸盐溶液，硼酸盐溶液等所有碱性材料；溶液通过加压或超声雾化器打散成微米至纳米级液滴，平均粒径 为1nm~2μm之间 ，并且通过气体管道与密闭脱酸装置相连。
上述方法中， 所述脱酸剂包括但不仅限于纳米 NaOH 粉体 ， Ca(OH)2 粉体， Cu(OH)2 粉体， Fe(OH)3 粉体， KOH 粉体 ， Na2CO3 粉体 或 NaHCO3 粉体、 乙二胺粉体等所有碱性粉体材料 。
上述方法中，所述的鼓风系统，是通过气体管道将纳米级碱性脱酸粉体材料或者超声换能器雾化的脱酸剂缓慢引入到密闭脱酸修复装置中，并且让系统内的脱酸剂循环，分布均匀。
上述方法中，控制体系内空气湿度保持在 10%~90% 。
上述方法中，所述的脱酸修复装置中有古籍 pH 监测，当被监测古籍 pH 达到 7~8.5 左右并维持 1~48 小时后，关闭系统。时间的长短取决于古籍的酸化程度和密封装置体积，古籍原始 pH 为 6~6.5 时，装置体积为待处理古籍总体积 1.5~2 倍时，脱酸维持 2~5 小时；原始 pH 每增加 0.2 ，脱酸维持时间减少 1~6h ；装置体积每增大一倍，脱酸维持时间增加 3~8h 。
与现有技术相比，本发明的优势在于：
无需很大的设备投入就可以大批量的处理酸化古籍；不破坏古籍原始的温度和湿度，不破坏纸张结构，不会对古籍造成二次损坏，可以很好的中和古籍中酸性物质，除酸效果明显。同时有一定的碱性物质残留在古籍中，更好的进一步延长了古籍的寿命。
附图说明
图1为发明 脱酸修复装置 的结构示意图；
图2为中间隔板的结构示意图；
图3为书架的结构示意图；
图4为本发明的气体流向图。
图中各个部件如下：
双开前门1、可视窗口2、积水槽3、风扇组4、湿度计5、除湿机6、真空泵7、压强计8、pH计9、灯10、中间隔板11、气体管道小孔12、背板13、超声雾化器14、气体管道15、PLC控制系统16、排水阀17、滑轮轨道18、书架19、出风口20。
具体实施方式
下面结合具体实施例对本发明作进一步地具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
本发明 脱酸修复装置结构如下 ，如图 1~ 图 4 所示， 脱酸修复装置 ，包括双开前门1、风扇组4、除湿机6、真空泵7、灯10、中间隔板11、气体管道小孔12、背板13、超声雾化器14、气体管道15和滑轮轨道18；所述装置的一面开设有双开前门1；所述中间隔板11将装置分割为上层和下层，所述上层与下层的底面均设置有风扇组4，所述装置中与装置门相对的背板13外表面上设置有除湿机6、真空泵7和超声雾化器14；所述中间隔板下部四周固定有灯10；所述气体管道15位于并贯穿于中间隔板11上层，且该段气体管道15上开有气体管道小孔12，所述气体管道15与超声雾化器14连接；所述装置底面上设置有滑轮轨道18。还包括可视窗口2，所述双开前门1两边和装置左右两侧有可视窗口2。还包括湿度计5、压强计8和pH计9；所述湿度计5、压强计8和pH计9均设置于装置内部。双开前门1上固定有PLC控制系统16，所述PLC控制系统，将风扇组4、除湿机6、真空泵7、超声雾化器14、灯10和书架19集成控制，通过监控湿度计5、压强计8、pH计9，实时控制灯开关，风扇启停、风速大小，除湿启停、除湿风量，真空泵启停、抽真空风速，超声雾化器启停、雾化量大小、书架转动启停、书架转动停留时间。所述装置由外层材料和内层材料组成，外层材料为碳钢，里层材料为不锈钢；装置总宽度为1m~2.5m，高度为1m~2.5m，长度为3m~12m。还包括积水槽3和排水阀17；所述下层底面上设置有积水槽3；所述积水槽3位于装置两侧和靠背板地面，所述积水槽3高度低于地面1~10cm，宽度为1~10cm；所述积水槽3和排水阀17连接；所述滑轮轨道13有两道，两道滑轮轨道13间的宽度与书架19宽度一致。所述中间隔板11上设置有出风口20，由于离风机近的部分流速较快，出风口面积离风扇组由近及远的方向依次增大。所述书架19为不锈钢材质，底部有滚轮；书架上装有不锈钢链条，书篮固定在链条上，链条由电机带动，电机开启后将书篮上下移动，从而使得书籍对气雾的吸收更加均匀；书篮为上微宽下微窄设计，古籍侧面可翻开边朝上放置，风扇组4从上至下的风使古籍略微打开，使脱酸剂渗透更均匀。
实施例1
取《医古书》-人民卫生出版社1937年版5本约0.004m3，取样测得书籍中纸张原始湿度约为8.6%，将书放入0.25m*0.25m*0.1m容积为0.00625m3的脱酸装置中，首先对体系进行抽湿，抽湿时间为4h，到达时间后关闭抽湿机。然后打开真空泵，将体系内压强抽到-0.05mpa后关闭真空泵。然后打开超声雾化器，脱酸剂选择NaOH固体和水按照质量比20:80的比例混合均匀，放入容器中，使用超声换能器将配好的NaOH溶液雾化，通过气体管道导入到密封容器内进行脱酸修复操作，通过控制气体管道阀门，将体系内空气湿度控制在50%左右，边中和纸张中的酸性物质边监测古籍的pH值；当被监测古籍pH达到7.2时，继续维持体系稳定2h，然后关闭系统。取样对比脱酸修复前后纸张性能平均值如下表：
PH 含水量% 抗张强度（KN/m） 耐破度 撕裂度（mN） 耐折度（次）
脱酸修复前 5.98 8.6 1.460 1.568 28 3
脱酸修复后 7.21 9.1 1.540 1.590 32 4
实施例2
取《医古书》-人民卫生出版社1937年版5本约0.004m3，取样测得书籍中纸张原始湿度约为9.2%，将书放入0.25m*0.25m*0.1m容积为0.00625m3的脱酸装置中，首先对体系进行抽湿，抽湿时间为3h，到达时间后关闭抽湿机。然后打开真空泵，将体系内压强抽到-0.07mpa后关闭真空泵。然后打开超声雾化器，脱酸剂选择NaOH固体和水按照质量比20:80的比例混合均匀，放入容器中，使用超声换能器将配好的NaOH溶液雾化，通过气体管道导入到密封容器内进行脱酸修复操作，通过控制气体管道阀门，将体系内空气湿度控制在50%左右，边中和纸张中的酸性物质边监测古籍的pH值；当被监测古籍pH达到7.2时，继续维持体系稳定2h，然后关闭系统。取样对比脱酸修复前后纸张性能平均值如下表：
PH 含水量% 抗张强度（KN/m） 耐破度 撕裂度（mN） 耐折度（次）
脱酸修复前 5.86 9.2 1.488 1.572 28 3
脱酸修复后 7.10 8.7 1.556 1.598 33 4
实施例3
取《医古书》-人民卫生出版社1937年版5本约0.004m3，取样测得书籍中纸张原始湿度约为7.3%，将书放入0.25m*0.25m*0.1m容积为0.00625m3的脱酸装置中，首先对体系进行抽湿，抽湿时间为4h，到达时间后关闭抽湿机。然后打开真空泵，将体系内压强抽到-0.05mpa后关闭真空泵。然后打开超声雾化器，脱酸剂选择NaOH固体和水按照质量比30:70的比例混合均匀，放入容器中，使用超声换能器将配好的NaOH溶液雾化，通过气体管道导入到密封容器内进行脱酸修复操作，通过控制气体管道阀门，将体系内空气湿度控制在50%左右，边中和纸张中的酸性物质边监测古籍的pH值；当被监测古籍pH达到7.2时，继续维持体系稳定2h，然后关闭系统。取样对比脱酸修复前后纸张性能平均值如下表：
PH 含水量% 抗张强度（KN/m） 耐破度 撕裂度（mN） 耐折度（次）
脱酸修复前 5.89 7.3 1.451 1.578 27 3
脱酸修复后 7.38 8.9 1.535 1.598 31 4
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种新型的古籍脱酸修复方法，其特征在于，首先将待处理的古籍放入密闭脱酸修复装置中，密封好后先后对系统进行抽湿操作和抽真空操作，使体系维持干燥，并且在负压下保持稳定后，开启 风扇组 ，通过气体管道直接将脱酸剂送至脱酸修复装置中，或先通过超声雾化器将碱性脱酸溶液雾化，然后将雾化后的碱性脱酸溶液再通过气体管道送至脱酸修复装置中，使待处理的古籍充分均匀地吸收碱性脱酸剂，同时对古籍 pH 监测，实现对古籍的脱酸修复；
    所述古籍包括处理古代酸性书本、档案、文献资料、图书、报刊、纸张、字画、棉和麻。
  2. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述装置体积与待处理的古籍总体积之间满足，装置体积：待处理的古籍总体积 =1.1:1~50:1 。
  3. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述抽湿操作，是通过抽湿机将体系内的空气湿度抽到 10%~90% ，并维持 2~24 小时；抽湿操作时间取决于古籍的原始湿度和密封装置体积，当古籍原始湿度为 8%~9% 时，装置体积为待处理古籍总体积 1.5~2 倍时，抽湿时间为 2~24h ；当原始湿度每减少 10% ，抽湿时间减少 2~6h ；当装置体积每增大一倍，抽湿时间增加 3~8h 。
  4. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述抽真空操作，是在抽湿操作完成后再进行的，通过真空泵将体系内压力抽到 0 至 -0.08mpa ；密闭体系维持稳定负压状态直至脱酸操作完成。
  5. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述的超声雾化器为超声换能器，将超声换能器放入装有脱酸剂的容器中，接通电源，通过压电陶瓷高频谐振，将脱酸剂结构分散而雾化成小分子的气雾。
  6. 根据权利要求 1 所述的纳米级脱酸剂，其特征在于，所述脱酸剂为纳米级碱性脱酸粉体材料、 碱性有机物溶液或碱性无机物溶液； pH值为7~13；所述 碱性脱酸溶液 包括 NaOH 溶液 ， Ca(OH)2 溶液 ， Cu(OH)2 溶液 ， Fe(OH)3 溶液 ， KOH 溶液 ， Na2CO3 溶液 ， NaHCO3 溶液 ， NH3·H2O 溶液，乙二胺溶液，磷酸盐溶液或硼酸盐溶液； 所述 碱性脱酸溶液 通过加压或超声雾化器打散成微米至纳米级液滴，平均粒径为1nm~2μm之间 。
  7. 根据权利要求 1 所述的纳米级脱酸剂，其特征在于， 所述脱酸剂粉末包括纳米 NaOH 粉体 ， Ca(OH)2 粉体， Cu(OH)2 粉体， Fe(OH)3 粉体， KOH 粉体 ， Na2CO3 粉体 或 NaHCO3 粉体或 乙二胺粉体 。
  8. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述的 风扇组 ，是通过气体管道将纳米级碱性脱酸粉体材料或者超声换能器雾化的脱酸剂缓慢引入到密闭脱酸修复装置中，并且让系统内的脱酸剂循环，分布均匀。
  9. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，控制体系内空气湿度保持在 10%~90% 。
  10. 根据权利要求 1 所述的古籍脱酸修复方法，其特征在于，所述的脱酸修复装置中有古籍 pH 监测，当被监测古籍 pH 达到 7~8.5 左右并维持 1~48 小时后，关闭系统；时间的长短取决于古籍的酸化程度和密封装置体积，当古籍原始 pH 为 6~6.5 时，装置体积为待处理古籍总体积 1.5~2 倍时，脱酸维持 2~5 小时；原始 pH 每增加 0.2 ，脱酸维持时间减少 1~6h ；装置体积每增大一倍，脱酸维持时间增加 3~8h 。
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