CN113863053A - Entire paper deacidification method - Google Patents
Entire paper deacidification method Download PDFInfo
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- CN113863053A CN113863053A CN202111159076.5A CN202111159076A CN113863053A CN 113863053 A CN113863053 A CN 113863053A CN 202111159076 A CN202111159076 A CN 202111159076A CN 113863053 A CN113863053 A CN 113863053A
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- deacidification
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- alternating current
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0063—Preservation or restoration of currency, books or archival material, e.g. by deacidifying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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Abstract
The invention discloses a deacidification method for whole book of paper, which deacidifies the whole book of books in three steps through prepressing, rapid deacidification and homogenization. On the basis of the static pressure entire deacidification method, the invention adds a homogenization process and improves the stability of the deacidification effect; high-voltage alternating current is used instead on the basis of the existing low-voltage direct current adsorption technology, so that the deacidification efficiency of the whole book is effectively improved, and the problem of uneven deacidification of the book caused by enrichment of anions and cations on a certain electrode is avoided. The deacidification method is convenient and fast to operate, environment-friendly in deacidification process, and capable of achieving accurate deacidification.
Description
Technical Field
The invention relates to the technical field of paper protection, in particular to a method for deacidifying whole volume of paper.
Background
The books are used as the most common carriers of the human intelligent crystals and play a vital role in the contents of scientific and technical preservation and the like; in human social life, books are still the most important means for spreading and learning knowledge. In libraries, archives and individual homes, tens of thousands of large documents are collected, and most of the books are paper documents. With the lapse of the service time, the storage conditions of the books are different, and the books are gradually aged and worn, so that the normal use of the books is influenced. Aging of books often accompanies yellowing and embrittlement of the paper, which is mainly due to gradual acidification of the paper under conditions of long-term use or improper storage. Therefore, in order to prolong the service life of books, the paper is often deacidified to prevent further aging. According to the specific requirements in the existing standard GB/T21712-2008 ancient book repair technical specification and quality requirement, the average pH range of the pages of the books is 7.5-10 after deacidification repair.
Patent CN 202110434579.2 discloses a plasma whole book paper deacidification device and process, and through a static pressure mode whole book deacidification method, after a slow release film prepared by a specific process is lined in a book to be deacidified, a deacidification agent is permeated into the paper to be deacidified through static pressure assisted by ultrasonic oscillation, so that thorough deacidification is realized. However, the static pressure time required by the process is long, further homogenization treatment is needed after the deacidification book leaves the machine, the process is complicated, the whole deacidification efficiency is low, and the condition of batch whole deacidification cannot be met.
Patent CN 201810461447.7 provides a method for deacidifying paper by an electro-adsorption method, which is a method for deacidifying paper by applying direct current by adding slow release films on both sides of the paper and placing the paper between inert electrode plates. The method has a certain effect on deacidification of single pages and a small amount of paper, but is not suitable for deacidification of the whole book, thickness nonuniformity of pages of books with more pages can be accumulated and amplified, when deacidification is used for paper clamping, the pages and the slow release film are difficult to completely joint, a punctiform or small-area air layer is easy to appear, the conductivity is poor, the current is low, and the deacidification efficiency is reduced; the thicker the book, the more severe this is. Meanwhile, the method mentioned above refers to that the inorganic acid radical ions are moved to the anode by applying direct current, however, for the acidified paper needing deacidification, the carboxylic acid ratio of the acidified paper is high due to oxidation under the influence of solar ultraviolet light or hydrolysis of cellulose, and most of the groups are bulky, so that the ions cannot be electrophoresed, and the moving speed is slow. Finally, due to the limitation of color feathering, color change and wrinkles in the paper, the water content of the paper deacidified by the method cannot be very high, and compared with a pure electrolyte solution, the water content of pages is low, and a large amount of solid exists, the weight is obstructed on an ion moving path, the migration speed is greatly reduced, the current is reduced, and the deacidification speed is slower.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problems solved by the present invention are: (1) the deacidification uniformity and the deacidification efficiency of the whole volume of paper are improved, the paper homogenization is completed, and the condition of acid return of the paper after deacidification is avoided; (2) the deacidification agent in the slow release film is easy to volatilize, so that the storage, transportation and lining requirements are too high; (3) the stability of the deacidification effect and the production efficiency are improved.
In the deacidification process in the prior art, a static pressure mode is used for deacidifying the whole book, after a slow release film prepared by a specific process is lined in a book to be deacidified, the deacidification agent is permeated into the paper to be deacidified by static pressure assisted with ultrasonic oscillation, and the complete deacidification is realized. However, the deacidification agent in the slow release film adopted by the method is only adsorbed in the holes of the slow release film, is easy to volatilize at normal temperature, needs to be kept in a sealed state in storage and transportation, and can pollute the environment in case of leakage; secondly, due to the characteristic of easy volatilization, in order to prevent the deacidification effect from being reduced due to the volatilization of the deacidification agent when the sustained-release membrane is sandwiched, the deacidification agent needs to be rapidly sandwiched in a sealed environment, and the requirements on the deacidification environment and the skill of operators are high.
The inventor finds that the deacidification agent is made into the inner core of the microcapsule, and the capsule wall made of the material inert to the deacidification agent completely isolates the deacidification agent from the air, so that the deacidification agent is prevented from volatilizing, the deacidification agent is also prevented from reacting with an acid substance in the air, and the storage stability of the deacidification agent is ensured. The microcapsule containing the deacidification agent is attached to a film or thin paper with certain strength through an adhesive to form a slow release film, during deacidification, pressure in a certain range is applied to the paper to be deacidified, which is lined with the slow release film, the microcapsule is broken under the pressure, the deacidification agent seeps out, and deacidification is performed on the paper.
The inventors have also found that the weak acid present in the paper is high and the neutralization reaction is slow; on the other hand, paper before deacidification originally contains water which occupies the pores of the paper to form acidic water, and after deacidification, the acidic water is neutralized by the diffusion of alkaline factors in the deacidification agent, so a homogenization process is needed to ensure that the deacidification reaction is complete and thorough and the deacidification effect is stable. The paper is kept at a certain temperature and moisture degree, which is beneficial to shortening the homogenization time.
The invention provides a deacidification method for whole volume of paper, which comprises the following steps:
s1, prepressing: lining the slow-release film in a whole book to be deacidified, fixing the whole book by a clamp, and then placing the clamp in a press; applying pressure, maintaining pressure and standing to finish prepressing;
s2 rapid deacidification: after the pre-pressing is finished, entering a rapid deacidification process, and applying current to the electrode plate on the clamp for deacidification;
s3 homogenization: after deacidification, the clamp is placed in a constant temperature and humidity box for homogenization; and (5) releasing the pressure of the clamp, and taking out the deacidification book to finish deacidification.
Preferably, the pre-pressing, rapid deacidification and homogenization processes are all carried out in a clamp pressure maintaining state.
Preferably, the sustained-release film in step S1 is a general sustained-release film.
Further preferably, the sustained-release membrane in step S1 may also be composed of microcapsules containing a deacidification agent and a film or tissue paper, and the microcapsules are bonded with the film or tissue paper by an adhesive; the mass ratio of the film or the tissue to the microcapsules is 1: (0.1-10).
Preferably, the film or the thin paper plays a supporting role, the material can be a polymer or paper material, and the size of the film or the thin paper can be cut at will to meet the deacidification requirements of paper with different sizes.
Preferably, the capsule wall of the microcapsule adopts inorganic or organic oil-soluble materials which are inert with deacidification agent; the inner core of the microcapsule can be prepared by adopting deacidification agents with different contents according to the deacidification requirement; the deacidification agent can be an aqueous solution deacidification agent or an organic solution deacidification agent.
Preferably, the crushing pressure range of the microcapsules is 0.2-10 kg/cm2(ii) a Further, the crushing pressure range is 0.6-2 kg/cm2。
Preferably, the diameter of the microcapsule ranges from 1 to 1000 μm.
Preferably, the pre-pressing designated time in the step S1 is 10-120 min.
Preferably, the magnitude of the applied pressure in step S1 is 0.1-5 kg/cm2。
Preferably, the current in step S2 is either a direct current or an alternating current.
Preferably, the voltage of the direct current is 4-36V.
Preferably, the voltage of the alternating current is 4-36V.
Preferably, the frequency of the alternating current is 0.01-50 Hz.
Preferably, the alternating current adopts any one of sine wave alternating current, cosine wave alternating current, square wave alternating current and triangular wave alternating current; further, the alternating current adopts square wave alternating current.
Preferably, the square wave alternating current includes the following conditions: under specific voltage, the power is conducted in the forward direction for a certain time T1 and in the reverse direction for a certain time T2, and T2 is more than or equal to T1.
Preferably, the set temperature of the constant temperature and humidity chamber in the step S3 is 40-80 ℃.
Preferably, the set humidity of the constant temperature and humidity chamber in step S3 is 70-95%.
Preferably, an insulating plate is arranged between the clamp and the electrode plate; further, the electrode plate is any one of a graphite inert electrode plate, a hydrophilic inert electrode plate and an oleophobic inert electrode plate.
The inventor finds that the maintenance of the stability of the ion electrophoresis under the action of the alternating current is the key of the rapid deacidification. After the electrode plate is contacted with water, the surface of the electrode plate is wetted by the water, and the wetting degree of each part of the surface of the electrode plate is different under the influence of factors such as gravity, contact angle and the like in the actual deacidification operation process; due to the difference, the actual active sites of the electrode plates are different, so that the stability of rapid deacidification is influenced, and the rapid deacidification cannot be performed once in serious cases, so that the damage to books is large. The inventor improves the method, and prepares a coating with good hydrophilicity and conductivity on the surface of the inert electrode to obtain the hydrophilic inert electrode plate. The hydrophilic inert electrode plate can be well wetted after being contacted with water, the stability of rapid deacidification is improved, deacidification can be performed at one time, and damage to books is reduced.
Preferably, the preparation method of the hydrophilic inert electrode plate is as follows:
x1, taking 1-2 parts by weight of magnesium nitrate, 8-16 parts by weight of nickel nitrate and 30-40 parts by weight of glycine, and dissolving in 300-500 parts by weight of water at 50-55 ℃ to obtain a solution A; calcining the solution A at 550-600 ℃ for 0.5-1 h under the protection of nitrogen to obtain a thermal decomposition product for later use;
taking 0.2-0.5 part by weight of the thermal decomposition product obtained in the step X1 from X2, and placing the thermal decomposition product on the surface of a reactor of vapor deposition equipment; ethylene is used as a carbon source, a vapor deposition method is used for preparing the multi-walled carbon nanotube, the introducing amount of argon in a reactor is 225-300 mL/min, the introducing amount of hydrogen is 125-150 mL/min, the vapor deposition temperature is 675-700 ℃, and the reaction time is 45-60 min; stopping introducing hydrogen after the reaction is finished, and cooling to normal temperature in an argon atmosphere to obtain the multi-walled carbon nanotube for later use;
x3, taking 2-5 parts by weight of the multiwall carbon nanotube obtained in the step X2, adding 75-100 parts by weight of a 5-8 mol/L sodium hydroxide aqueous solution, firstly ultrasonically dispersing for 3-5 min at the frequency of 30-50 KHz, then stirring for 2-4 h at the speed of 900-1200 rpm at the temperature of 80-90 ℃, filtering to obtain a filter cake, and washing for 3-5 times to obtain the carboxyl multiwall carbon nanotube; adding 10-25 parts of aqueous solution of polyvinyl alcohol with the concentration of 8-12 wt% into the carboxyl multi-walled carbon nano tube, and performing ultrasonic dispersion for 10-15 min at the frequency of 30-50 KHz to obtain a carboxyl multi-walled carbon nano tube mixed solution for later use;
x4, mixing the multi-wall carbon nano tube obtained by the method in the step X2, porous graphite and polyvinylidene fluoride in a mass ratio of 1: (1.8-2.8): (7.5-12) mixing to obtain a mixed board pressing raw material, and carrying out hot pressing on the mixed board pressing raw material at the temperature of 170-200 ℃ for 10-15 min under the pressure of 12-20 MPa to obtain a hot pressing board, wherein the thickness of the hot pressing board is 1-3 mm; mixing 8-12 parts of the carboxyl multi-walled carbon nanotube mixed solution obtained in the step X3, 0.4-0.8 part of glutaraldehyde and 0.3-0.5 part of hydrochloric acid with the mass concentration of 38 wt%, and then spraying the mixture of the three parts on one surface of a hot pressing plate, wherein the loading density is 0.42-0.86 mg/cm2And after spraying, crosslinking for 0.5-2 hours at 65-80 ℃, and coating the coating with the thickness of 0.2-0.5 mm to obtain the hydrophilic inert electrode plate.
In production practice, the inventor finds that the hydrophilic inert electrode plate can improve the stability of rapid deacidification, but the surface of the electrode plate can be polluted by oil stains after being used for many times, the oil stains are assisted with the surface of the electrode plate and are gathered locally, the service life of the electrode plate is shortened, and the situation is particularly obvious when deacidifying books with a long age. Due to pollution of oil stains, the electrode plate needs to be frequently replaced and cleaned, and the deacidification efficiency is seriously influenced; therefore, the inventors have found that the pigment on the book is mainly attached to the fibers through the binder, and when the book is aged, the internal fibers become loose from the original dense structure, and the bonding with the binder is reduced. The binder is mainly lipophilic substances such as polyamide resin and the like, is dispersed in water, and electrophoreses to the surface of the electrode plate under the action of alternating current to aggregate, so that oil stains which are difficult to fall off are formed over time, and the service life of the electrode plate is shortened. Aiming at the technical problem, the inventor further optimizes the electrode plate and introduces a fluorocarbon short chain structure into the hydrophilic coating; because the polarity of the fluorocarbon bond is strong, and the interaction between the connecting material and the polar group is weak, the connecting material is difficult to adhere to the surface of the electrode plate, and the generation of oil stains is reduced; meanwhile, the interaction between water molecules and polar groups is strong, and the hydrophilicity of the electrode plate can be further improved by the fluorocarbon short chain structure.
Preferably, the preparation method of the oleophobic inert electrode plate is as follows:
y1 is prepared by dissolving 1-2 parts by weight of magnesium nitrate, 8-16 parts by weight of nickel nitrate and 30-40 parts by weight of glycine in 300-500 parts by weight of water at 50-55 ℃ to obtain solution A; calcining the solution A at 550-600 ℃ for 0.5-1 h under the protection of nitrogen to obtain a thermal decomposition product for later use;
y2, taking 0.2-0.5 part by weight of thermal decomposition product obtained in the step Y1, and placing the thermal decomposition product on the surface of a reactor of vapor deposition equipment; ethylene is used as a carbon source, a vapor deposition method is used for preparing the multi-walled carbon nanotube, the introducing amount of argon in a reactor is 225-300 mL/min, the introducing amount of hydrogen is 125-150 mL/min, the vapor deposition temperature is 675-700 ℃, and the reaction time is 45-60 min; stopping introducing hydrogen after the reaction is finished, and cooling to normal temperature in an argon atmosphere to obtain the multi-walled carbon nanotube for later use;
y3 is prepared by dissolving 28-35 parts by weight of poly (ethylene glycol) methacrylate and 22-26 parts by weight of N-methylperfluorohexylsulfonamide-ethyl acrylate in 120-180 parts by weight of N, N-dimethylformamide to obtain a solution B; dissolving 3-5 parts of azodiisobutyronitrile in 30-50 parts of N, N-dimethylformamide to obtain a solution C; heating the solution B to 40-45 ℃ under the protection of nitrogen, adding the solution C, continuously heating to 75-80 ℃, mixing and reacting at a stirring speed of 600-900 rpm for 12-24 hours, cooling to normal temperature after the reaction is finished, and evaporating the solvent under reduced pressure to obtain a short-chain fluorinated polymer for later use;
y4, taking 2-5 parts by weight of the multiwalled carbon nanotube obtained in the step Y2, adding 75-100 parts by weight of a 5-8 mol/L sodium hydroxide aqueous solution, firstly ultrasonically dispersing for 3-5 min at the frequency of 30-50 KHz, then stirring for 2-4 h at the speed of 900-1200 rpm at the temperature of 80-90 ℃, filtering to obtain a filter cake, and washing for 3-5 times to obtain the carboxyl multiwalled carbon nanotube; adding 10-25 parts of aqueous solution of polyvinyl alcohol with the concentration of 8-12 wt% into a carboxyl multi-walled carbon nanotube, and performing ultrasonic dispersion for 10-15 min at the frequency of 30-50 KHz to obtain a carboxyl multi-walled carbon nanotube mixed solution; mixing the carboxyl multi-walled carbon nanotube mixed solution and the short-chain fluorinated polymer obtained in the step Y3 at a speed of 360-720 rpm for 30-45 min to obtain a polymer coating for later use;
y5, mixing the multi-wall carbon nano tube obtained by the method of the step Y2, porous graphite and polyvinylidene fluoride in a mass ratio of 1: (1.8-2.8): (7.5-12) mixing to obtain a mixed board pressing raw material, and carrying out hot pressing on the mixed board pressing raw material at the temperature of 170-200 ℃ for 10-15 min under the pressure of 12-20 MPa to obtain a hot pressing board, wherein the thickness of the hot pressing board is 1-3 mm; mixing 8-12 parts of the polymer coating obtained in the step Y4, 0.4-0.8 part of glutaraldehyde and 0.3-0.5 part of hydrochloric acid with the mass concentration of 38 wt%, and spraying the mixture of the three parts on one surface of a hot pressing plate, wherein the loading density is 0.42-0.86 mg/cm2And after spraying, crosslinking for 0.5-2 hours at 65-80 ℃, and coating the coating with the thickness of 0.2-0.5 mm to obtain the oleophobic inert electrode plate.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The invention has the beneficial effects that:
compared with the prior art, the paper deacidification method improves the uniformity and deacidification efficiency of deacidification of the whole volume of paper, completes paper homogenization and avoids the condition of acid return of the deacidified paper.
Compared with the prior art, the invention solves the problem of high requirements on storage, transportation and lining caused by easy volatilization of the deacidification agent in the sustained-release membrane.
Compared with the prior art, the method has the advantages that alternating current is selectively applied, anions and cations are not enriched on a certain polar plate by changing the method of the cathode and the anode, the problem that the alkalinity of the cathode is enhanced due to the electrolytic reaction of water at the polar plate is solved, the pH of paper close to the cathode is too high, and the potential hazard of cellulose alkaline hydrolysis exists; solves the technical problem that the acidity of the anode becomes stronger and is contrary to the aim of deacidification.
Compared with the prior art, the electrode plate used by the invention can improve the stability of the deacidification effect; and the problem of adhesion of oil stains is effectively solved, the replacement frequency and the cleaning difficulty of the electrode plate are reduced, and the production efficiency is improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Book "science and Life View", 89 pages total, machine made paper, quantitative 50g/m2A5 size, original pH 5.5, lining sustained release membrane at a rate of 0.4kg/cm2Applying direct current after the static pressure of the pressure is 10min, wherein the forward energization time is 4min, the reverse energization time is 4min, the voltage is 20V, and the deacidification time is 16 min; the temperature and the humidity of the precise constant temperature and humidity box are 50 ℃, the humidity is 90 percent, and the homogenization time is 120 min; after deacidification, the average pH value is 9.3, the paper has no folds and has no fading phenomenon.
The slow release film is prepared by adsorbing a calcium water-based deacidification agent by water absorption paper with the thickness of 0.2 mm; the absorbent paper has an absorbent capacity of 2 times its own weight.
The electrode plate is a graphite inert electrode plate.
Example 2
Book, Chun-autumn left handed Manual, 36 pages in total, hand made paper, quantitative 20g/m2A4 size, original pH 4.3, lining sustained release membrane at a rate of 0.4kg/cm2Applying cosine alternating current after the static pressure of the pressure is 30min, wherein the voltage is 20V, the alternating current frequency is 30Hz, and the deacidification time is 25 min; homogenizing at 45 deg.C and 90% humidity for 60 min; after deacidification is finished, the average pH value is 8.5, the paper has no folds and does not fade.
The slow release film is prepared by adsorbing a calcium water-based deacidification agent by water absorption paper with the thickness of 0.2 mm; the absorbent paper has an absorbent capacity of 2 times its own weight.
The electrode plate is a graphite inert electrode plate.
Example 3
Book mathematical physical equation and special function, total 83 pages, machine made paper, quantitative 56g/m2A5 size, original pH 3.9, lining sustained release membrane at a rate of 0.4kg/cm2After the pressure static pressure is 40min, square wave alternating current with the voltage of 36V is applied, the alternating current frequency is 30Hz, and the deacidification time is 24 min; the temperature and humidity of the precise constant temperature and humidity box are 55 ℃, the humidity is 90 percent, and the homogenization time is 90 min; the average pH value after deacidification is 8.4, the paper has no folds and no fading conditionThe method is described.
The slow release film is prepared by adsorbing a calcium water-based deacidification agent by water absorption paper with the thickness of 0.2 mm; the absorbent paper has an absorbent capacity of 2 times its own weight.
The electrode plate is a graphite inert electrode plate.
Example 4
Book "Alijie to Shang (English edition), 154 pages total, machine made paper, quantitative 75g/m2A5 size, original pH 4.5, lining sustained release membrane at a rate of 0.4kg/cm2After 60min of pressure static pressure, applying 12V sine alternating current, deacidifying for 60min, wherein the frequency of the alternating current is 30 Hz; the temperature and the humidity of the precise constant temperature and humidity box are 55 ℃, the humidity is 90 percent, and the homogenization time is 120 min; the average pH after deacidification was 9.2, the paper had no wrinkles and no fading occurred.
The slow release film is prepared by adsorbing a calcium water-based deacidification agent by water absorption paper with the thickness of 0.2 mm; the absorbent paper has an absorbent capacity of 2 times its own weight.
The electrode plate is a graphite inert electrode plate.
Comparative example 1
The equipment and parameters used in this comparative example were the same as in example 2, except that: the comparative example was applied with no voltage and the results are shown in table 1, indicating that application of voltage helps to improve deacidification efficiency. The books used in example 2 and comparative example 1 were two books collected in the same collection in the same batch "left handed passage of spring and autumn", with a total of 36 pages, handmade paper, basis weight 20g/m2A4 size, original pH 4.3.
TABLE 1
In the protection of books, the acidic environment is not favorable for the preservation of paper, so the acidity of the paper is reduced after deacidification treatment, and the average pH is correspondingly increased. As seen by comparing example 2 with comparative example 1, comparative example 1 has no voltage applied and is weakly acidic after deacidification; example 2 application of a voltage to deacidify at an average pH of 8.7 helped to increase deacidification efficiency.
Comparative example 2
The equipment and parameters used in this comparative example were the same as in example 4, except that: in the comparative example, the constant temperature and humidity homogenization treatment is not performed after deacidification, and the test results are shown in table 2, which shows that the homogenization treatment can improve the stability of the deacidification effect. Example 2 and comparative example 1 the book used was two Alijie to mountain departed (English edition) collected in the same collection in the same batch, 154 pages total, machine made paper, basis weight 75g/m2A5 size, original pH 4.5.
TABLE 2
Maintaining the stability of the pH of the deacidified paper is beneficial for book protection, and longer deacidification time indicates better stability after deacidification. As can be seen from the comparison, in example 4, the reduction of the pH value is lower than that of comparative example 2 after the homogenization treatment, which indicates that the homogenization is favorable for improving the stability of the deacidification effect.
Example 5
Book Zhouyitong Yi (Zhouyitong Yi)2A5 size, original pH 3.7, lining sustained release membrane at 0.4kg/cm2Applying square wave alternating current with the voltage of 36V after the pressure static pressure of 40min, and the deacidification time is 27 min; the temperature and humidity of the precise constant temperature and humidity box are 55 ℃, the humidity is 90 percent, and the homogenization time is 90 min; after deacidification, the average pH was 7.8, the paper had no wrinkles and no fading occurred.
The slow release film is prepared by adsorbing a calcium water-based deacidification agent by water absorption paper with the thickness of 0.2 mm; the absorbent paper has an absorbent capacity of 2 times its own weight.
The electrode plate is a graphite inert electrode plate.
Example 6
Example 6 the book used in example 5 was one of 6 book Zhouyitong of the same collection of books in the same collection, 127 pages total, machine made paper, basis weight 68g/m2A5 size, original pH 3.7, lining sustained release membrane at 0.4kg/cm2After 40min of hydrostatic pressureApplying square wave alternating current with the voltage of 36V, and the deacidification time is 27 min; the temperature and humidity of the precise constant temperature and humidity box are 55 ℃, the humidity is 90 percent, and the homogenization time is 90 min; after deacidification, the average pH value is 8.3, the paper has no folds and fading does not occur.
The slow release film consists of microcapsules containing a deacidification agent and thin paper, and the microcapsules and the thin paper are bonded through an adhesive; the diameter of the microcapsule containing the deacidification agent (provided by Hefei Rexue New Material science and technology Co., Ltd.) is 200 μm, the wall material is dextrin, the deacidification agent is a magnesium hydroxide aqueous solution with the mass concentration of 8 wt%, the wrapping rate is 80%, and the extrusion breaking pressure is 0.4kg/cm2(ii) a The thin paper is absorbent paper with the thickness of 0.2mm, and the mass ratio of the absorbent paper to the microcapsules is 1: 2, bonding the two by using the water-based acrylic resin.
TABLE 3
| Average pH before Deacidification | Average pH after Deacidification | |
| Example 5 | 3.7 | 7.8 |
| Example 6 | 3.7 | 8.3 |
Example 7
In substantial agreement with example 6, the book used was one of 6 book Zhouyitong of the same collection in the same collection as example 6, except that the electrode plates used were replaced with hydrophilic inert electrode plates from ordinary graphite inert electrode plates; the preparation method of the hydrophilic inert electrode plate comprises the following steps:
x1 dissolving 1.5kg of magnesium nitrate, 12kg of nickel nitrate and 36kg of glycine in 325kg of water at 55 ℃ to obtain a solution A; putting the solution A into a heating device, calcining for 0.5h at 575 ℃ under the protection of nitrogen to obtain a thermal decomposition product for later use;
x2 putting 0.3kg of thermal decomposition product obtained in the step X1 on the surface of a reactor of vapor deposition equipment; ethylene is used as a carbon source, a vapor deposition method is used for preparing the multi-walled carbon nanotube, the introducing amount of argon in a reactor is 225mL/min, the introducing amount of hydrogen is 125mL/min, the vapor deposition temperature is 675 ℃, and the reaction time is 60 min; stopping introducing hydrogen after the reaction is finished, and cooling to normal temperature in an argon atmosphere to obtain the multi-walled carbon nanotube for later use;
x3 is calculated by weight parts, 3.5kg of the multi-walled carbon nano-tube obtained in the step X2 is added with 75kg of sodium hydroxide aqueous solution with the concentration of 6mol/L, firstly, ultrasonic dispersion is carried out for 4min at the frequency of 50KHz, then, stirring is carried out for 3h at the speed of 900rpm at the temperature of 90 ℃, a filter cake is obtained by filtration, and washing is carried out for 3 times to obtain the carboxyl multi-walled carbon nano-tube; adding 18kg of aqueous solution of polyvinyl alcohol with the concentration of 8 wt% into the carboxyl multi-walled carbon nano-tube, and performing ultrasonic dispersion for 10min at the frequency of 50KHz to obtain a carboxyl multi-walled carbon nano-tube mixed solution for later use;
x4, taking 2.5kg of multi-walled carbon nanotubes obtained by the method in the step X2, porous graphite and polyvinylidene fluoride according to the mass ratio of 1: 1.8: 7.5, mixing to obtain a mixed board pressing raw material, and carrying out hot pressing on the mixed board pressing raw material at 16MPa and 170 ℃ for 15min to obtain a hot pressing board, wherein the thickness of the hot pressing board is 2 mm; mixing 8kg of the carboxyl multi-walled carbon nanotube mixed solution obtained in the step X3, 0.4kg of glutaraldehyde and 0.3kg of hydrochloric acid with the mass concentration of 38 wt%, and spraying the mixture of the three on one surface of a hot pressing plate with the loading density of 0.42mg/cm2And after spraying, crosslinking for 2 hours at 65 ℃ to obtain a hydrophilic inert electrode plate, wherein the thickness of the coating is 0.3 mm.
TABLE 4
| Average pH before Deacidification | Average pH after Deacidification | |
| Example 6 | 3.7 | 8.3 |
| Example 7 | 3.7 | 8.9 |
Example 8
In substantial agreement with example 6, the book used was one of 6 book Zhouyitong of the same collection in the same collection as example 6, except that the electrode plates used were replaced with oleophobic inert electrode plates from ordinary graphite inert electrode plates; the preparation method of the oleophobic inert electrode plate comprises the following steps:
y1 dissolving 1.5kg of magnesium nitrate, 12kg of nickel nitrate and 36kg of glycine in 325kg of water at 55 ℃ to obtain a solution A; putting the solution A into a heating device, calcining for 0.5h at 575 ℃ under the protection of nitrogen to obtain a thermal decomposition product for later use;
y2 putting 0.3kg of thermal decomposition product obtained in step X1 on the surface of a reactor of vapor deposition equipment; ethylene is used as a carbon source, a vapor deposition method is used for preparing the multi-walled carbon nanotube, the introducing amount of argon in a reactor is 225mL/min, the introducing amount of hydrogen is 125mL/min, the vapor deposition temperature is 675 ℃, and the reaction time is 60 min; stopping introducing hydrogen after the reaction is finished, and cooling to normal temperature in an argon atmosphere to obtain the multi-walled carbon nanotube for later use;
y3 in parts by weight, 28kg of poly (ethylene glycol) methacrylate and 22kg of ethyl acrylate (N-methylperfluorohexylsulfonamide) were dissolved in 120kg of N, N-dimethylformamide to obtain a solution B; dissolving 3.5kg of azobisisobutyronitrile in 35kg of N, N-dimethylformamide to obtain a solution C; heating the solution B to 42 ℃ under the protection of nitrogen, then adding the solution C, continuously heating to 75 ℃, mixing and reacting at a stirring speed of 600rpm for 12 hours, cooling to normal temperature after the reaction is finished, and evaporating the solvent under reduced pressure to obtain a short-chain fluorinated polymer for later use;
y4 is calculated by weight, 3.5kg of the multiwall carbon nanotube obtained in the step Y2 is added with 75kg of sodium hydroxide aqueous solution with the concentration of 6mol/L, firstly, ultrasonic dispersion is carried out for 4min at the frequency of 50KHz, then, stirring is carried out for 3h at the speed of 900rpm at the temperature of 90 ℃, a filter cake is obtained by filtration, and washing is carried out for 3 times, thus obtaining the carboxyl multiwall carbon nanotube; adding 18kg of aqueous solution of polyvinyl alcohol with the concentration of 8 wt% into the carboxyl multi-walled carbon nano-tube, and performing ultrasonic dispersion for 10min at the frequency of 50KHz to obtain a carboxyl multi-walled carbon nano-tube mixed solution; mixing the carboxyl multi-walled carbon nanotube mixed solution and the short-chain fluorinated polymer obtained in the step Y3 at the speed of 720rpm for 30min to obtain a polymer coating for later use;
and Y5, taking 2.5kg of the multi-wall carbon nano tube obtained by the method of the step Y2, the porous graphite and the polyvinylidene fluoride according to the mass ratio of 1: 1.8: 7.5, mixing to obtain a mixed board pressing raw material, and carrying out hot pressing on the mixed board pressing raw material at 16MPa and 170 ℃ for 15min to obtain a hot pressing board, wherein the thickness of the hot pressing board is 2 mm; 8kg of the polymer coating obtained in step Y4 were mixed with 0.4kg of glutaraldehyde and 0.3kg of hydrochloric acid having a concentration of 38% by weight, and the mixture was sprayed onto one side of a hot pressboard at a loading density of 0.42mg/cm2And after spraying, crosslinking for 2 hours at 65 ℃ and obtaining the oleophobic inert electrode plate, wherein the thickness of the coating is 0.3 mm.
TABLE 5
| Average pH before Deacidification | Average pH after Deacidification | |
| Example 7 | 3.7 | 8.9 |
| Example 8 | 3.7 | 9.4 |
Test example 1
The hydrophilicity and the oleophobic property of the common graphite inert electrode, the hydrophilic inert electrode plate and the oleophobic inert electrode plate in the embodiments 6 to 8 were tested. Sandingand SDC-200 research type full-automatic contact angle measuring instrument (precision instruments ltd. Huashitong, mountain city) was used to test the contact angles of water and oil on the surface of the electrode plate, 5 groups of samples were prepared for each group of examples or comparative examples, and the results were averaged. The results of the hydrophilicity and lipophobicity type tests are shown in Table 6.
TABLE 6
| Water contact Angle (°) | Oil contact Angle (°) | |
| Example 6 | 93 | 76 |
| Example 7 | 42 | 81 |
| Example 8 | 31 | 142 |
The magnitude of the contact angle reflects the degree of wetting of water or oily substances on the surface of the material. As can be seen by comparing the examples 6-8, the electrode plate prepared in the example 8 has good hydrophilic and oleophobic properties, and can meet the requirements of the invention. The reason for this may be that example 8 introduces fluorocarbon short chain structure in the hydrophilic coating; because the polarity of the fluorocarbon bond is strong, and the interaction between the connecting material and the polar group is weak, the connecting material is difficult to adhere to the surface of the electrode plate, and the generation of oil stains is reduced; meanwhile, the interaction between water molecules and polar groups is strong, and the hydrophilicity of the electrode plate can be further improved by the fluorocarbon short chain structure.
Some of the raw material parameters in the comparative examples and examples of the present invention are as follows:
poly (ethylene glycol) methacrylate, available from Shanghai future industries, Inc., CAS number: 25736-86-1;
acrylic acid (N-methylperfluorohexylsulfonamide) ethyl ester, Anhui chemical Co., Ltd, CAS No.: 67584-57-0;
azobisisobutyronitrile, denna yuba chemical limited, CAS No.: 78-67-1;
chemical vapor deposition system, KJ-T1050-CVD-LZ, Zhengzhou Kejia electric furnace Co.
The preparation method of the calcium-based aqueous deacidification agent comprises the following steps: mixing 8g of nano Ca (OH)2Dissolving in 1L80 wt% ethanol water solution, and mixing.
Claims (9)
1. A deacidification method for whole volume of paper is characterized by comprising the following steps:
s1, prepressing: lining the slow-release film in a whole book to be deacidified, fixing the whole book by a clamp, and then placing the clamp in a press; applying pressure, maintaining pressure and standing to finish prepressing;
s2 rapid deacidification: after the pre-pressing is finished, entering a rapid deacidification process, and applying current to the electrode plate on the clamp for deacidification;
s3 homogenization: after deacidification, placing the clamp together with the whole book into a constant temperature and humidity box for homogenization; and (5) releasing the pressure of the clamp, and taking out the deacidification book to finish deacidification.
2. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: and the pre-pressing time in the step S1 is 10-120 min.
3. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: the magnitude of the applied pressure is 0.1-5 kg/cm2。
4. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: in the step S2, the current is direct current, and the voltage is 4-36V.
5. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: in the step S2, the current is an alternating current, the voltage is 4-36V, and the frequency is 0.01-50 Hz.
6. The method of deacidifying an entire sheet of paper as claimed in claim 5, wherein: the alternating current adopts any one of sine wave alternating current, cosine wave alternating current, square wave alternating current and triangular wave alternating current.
7. The method of deacidifying an entire sheet of paper as claimed in claim 5, wherein: the alternating current adopts square wave alternating current.
8. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: and S3, setting the temperature of the constant temperature and humidity box to be 40-80 ℃.
9. A method of deacidifying an entire sheet of paper as claimed in claim 1, wherein: and step S3, setting the humidity of the constant temperature and humidity box to be 70-95%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114934403A (en) * | 2022-05-18 | 2022-08-23 | 杭州众材科技股份有限公司 | Paper bacteriostatic deacidification agent, preparation method and application |
| CN117107548A (en) * | 2023-08-01 | 2023-11-24 | 南京大学 | Preparation method and application of composite deacidification material with high alkali reserve and hydrophobicity after deacidification treatment of paper |
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| CN114934403A (en) * | 2022-05-18 | 2022-08-23 | 杭州众材科技股份有限公司 | Paper bacteriostatic deacidification agent, preparation method and application |
| CN117107548A (en) * | 2023-08-01 | 2023-11-24 | 南京大学 | Preparation method and application of composite deacidification material with high alkali reserve and hydrophobicity after deacidification treatment of paper |
| CN117107548B (en) * | 2023-08-01 | 2024-02-09 | 南京大学 | Preparation method and application of composite deacidification material with high alkali reserve and hydrophobicity after deacidification treatment of paper |
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