CN107574709B - Method for repairing paper document by layer-by-layer self-assembly film forming technology - Google Patents
Method for repairing paper document by layer-by-layer self-assembly film forming technology Download PDFInfo
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Abstract
The invention discloses a method for repairing a paper document by utilizing a layer-by-layer self-assembly film forming technology. The method utilizes a layer-by-layer self-assembly film forming technology to form a film on the surface of the paper to be repaired, so as to realize paper repair. The method comprises the following specific steps: and alternately depositing a water-soluble chitosan assembly layer and a carboxymethyl cellulose sodium salt assembly layer on the surface of the paper to be repaired to obtain the self-assembly composite film of the water-soluble chitosan and carboxymethyl cellulose layers. The invention is applied to the reinforcement and restoration of paper documents by adopting a layer-by-layer self-assembly technology for the first time. The color difference of the paper after the reinforcement and repair is not changed, the appearance of the paper is as old as the old, and the strength and the folding endurance of the paper are obviously improved; the hydrophobic property is obviously improved, the swelling effect of the invasion of water on the cellulose can be prevented, and the hydrolysis of the cellulose is reduced; the hydrophobic surface of the paper effectively reduces the attachment of microorganisms, and the chitosan layer inhibits the growth of the microorganisms, so that the condition of damage by worms and corrosion of the paper is reduced.
Description
Technical Field
The invention belongs to the field of chemistry, relates to reinforcement and deacidification of paper files, and particularly relates to a method for repairing a paper document by using a layer-by-layer self-assembly film forming technology.
Background
The paper cultural relic file is a valuable cultural heritage left by ancestors to us, is a carrier and a witness inherited by Chinese history, and has important historical material value, artistic value and cultural relic value. The cultural relics are protected in the present generation and are beneficial to the thousand autumn. However, the ancient book status in China is not optimistic. Most of the existing paper ancient books and archives are generally damaged by aging and acidification of paper, and especially, the existing documents are much less and less because the existing documents can be preserved. Therefore, better protection of precious documents is an urgent and arduous task in front of us.
The ancient book paper mainly comprises cellulose, and acid is a catalyst for cellulose hydrolysis, and cellulose is easy to undergo hydrolysis reaction under acidic conditions. The vegetable cellulose is oxidized and hydrolyzed to produce easily crushed oxidized fiber and sulfurous acid. Sulfurous acid has a bleaching effect, can fade leaves, belongs to an extremely unstable compound, and can generate stable sulfuric acid after absorbing oxygen in air. After hydrolysis of cellulose, the degree of polymerization decreases, producing hydrolyzed cellulose, which causes the paper to turn yellow and become brittle. When the degree of polymerization of cellulose after hydrolysis drops below 200, the paper becomes too brittle to read.
Since the cellulose of the acidified paper has been largely destroyed, the mechanical properties of the paper have been reduced to a large extent. The necessary strengthening of the paper is therefore necessary. At present, the reinforcing and protecting method for paper cultural relics mainly comprises a mounting method, a film adding method, a silk screen reinforcing method, a glue solution reinforcing method and the like. The methods are 'temporary solution and permanent solution', and can not really improve the mechanical property of paper from the chemical perspective. Moreover, the paper strengthening method is time-consuming and labor-consuming, and has low efficiency.
Disclosure of Invention
The invention aims to provide a method for repairing a paper document, which adopts a layer-by-layer self-assembly film forming technology to reinforce and repair the paper document, the color difference of paper after reinforcement and repair is not changed, the appearance is as old as the old, and the strength and the folding endurance of the paper are obviously improved.
The method for repairing the paper document provided by the invention utilizes a layer-by-layer self-assembly film forming technology to form a film on the surface of the paper to be repaired, thereby realizing paper repair. The paper document to be repaired can be paper in various forms, such as acid paper, modern paper, handmade paper, mechanical paper, newspaper, single-page paper, page paper or books, and the material can be cellulose.
The method may specifically comprise the steps of: and alternately depositing a water-soluble chitosan assembly layer and a carboxymethyl cellulose sodium salt assembly layer on the surface of the paper to be repaired to obtain the self-assembly composite film of the water-soluble chitosan and carboxymethyl cellulose layers. The water-soluble chitosan is preferably a water-soluble chitosan salt, including but not limited to: chitosan hydrochloride, chitosan quaternary ammonium salt, chitosan glutamate, chitosan lactate and the like.
The thickness of the self-assembled composite film of the water-soluble chitosan and carboxymethyl cellulose layer can be 50-400 nm, and specifically can be 70-240 nm, 100-170 nm, 170-240 nm, 70nm, 140nm, 100nm, 170nm or 240 nm. The number of self-assembly layers of the water-soluble chitosan and carboxymethyl cellulose laminated self-assembly composite film can be 1-10, preferably 3-6, and specifically 1-3; in each self-assembly layer, the thickness of the water-soluble chitosan assembly layer can be 30-80 nm, such as 35nm, and the thickness of the carboxymethyl cellulose sodium salt assembly layer can be 30-80 nm, such as 35 nm. The temperature of the alternate deposition can be 25-50 ℃, particularly 30 ℃, and the time can be 0.1-1 hour, which is determined according to the number of self-assembly layers.
In the method, the film forming material permeates the surface of the paper to be repaired by a vacuum permeation method. The vacuum infiltration method comprises the following specific operations: and laying the paper to be repaired on the porous support plate, and alternately performing controllable vacuum filtration on the water-soluble chitosan aqueous solution and the sodium carboxymethyl cellulose saline aqueous solution.
The concentrations of the water-soluble chitosan aqueous solution and the sodium carboxymethyl cellulose aqueous solution are both 0.8-1.5 mg/mL, and specifically can be 1.0 mg/mL. In the process of each deposition, the volume of the water-soluble chitosan aqueous solution and the volume of the sodium carboxymethyl cellulose saline solution are not required, and the surface of the paper to be repaired is ensured to be exactly paved in the specific implementation process. The pH value of the sodium carboxymethylcellulose aqueous solution can be 7.5-7.8, and with the formation of the self-assembled film, the mechanical property of the paper is greatly improved, and the sodium carboxymethylcellulose attached to the surface of the paper provides a certain alkali reserve for the repaired paper, so that the further invasion of acid is prevented. The aperture ratio of the porous support plate can be 0.5-1.5%, the pores are uniformly distributed on the porous support plate, and the pore diameter can be 0.05-0.1 mm.
The vacuum infiltration adopts the following devices: the device comprises a spraying system, a self-assembly reaction system and a vacuum filtration system; the self-assembly reaction system is a reaction tank, and a porous support plate for placing paper to be repaired is horizontally arranged on the reaction tank; the spraying system is positioned above the porous supporting plate and is used for spraying self-assembly feed liquid on the paper to be repaired; and the vacuum filtration system is connected with the side wall of the reaction tank below the porous support plate and is used for enabling the self-assembly liquid to permeate the paper to be repaired, forming a film on the surface of the paper to be repaired and drying the film.
The reaction tank can be provided with a temperature control heater to control the temperature of the reaction tank and provide proper conditions for the self-assembly reaction of the surface of the paper to be repaired.
The spraying system can comprise a spray head and a spraying distribution plate, and the spraying distribution plate and the porous support plate are arranged in parallel so that the self-assembly liquid is uniformly sprayed on the surface of the paper to be repaired.
The spraying system can also comprise an annular overflow groove which is positioned between the spraying distribution plate and the side wall of the reaction tank and is used for collecting redundant self-assembly feed liquid or cleaning liquid.
The vacuum filtration system comprises a vacuum pump and a vacuum control system, the vacuum pump and the vacuum control system provide proper vacuum degree for the space below the porous support plate in the reaction tank, so that the self-assembly liquid permeates the paper to be repaired, and the vacuum degree can be flexibly adjusted according to the type of the paper to be repaired. The cold trap is arranged to facilitate condensation of water vapor, and water vapor is not brought into the vacuum pump as far as possible.
The device also comprises a cleaning system for cleaning the membrane, the cleaning system is connected with the spraying system, cleaning liquid in the cleaning system is sprayed on the surface of the membrane of the paper to be repaired through the spraying system, and the cleaning liquid permeates the membrane under the action of the vacuum filtration system, so that the membrane can be cleaned.
In the above method, the alternating deposition may further include depositing a layer of metal oxide Ti0 on the surface of the paper sheet to be repaired2A step of gel film (which may function to activate the cellulose surface). The gold isMetal oxide Ti02The gel film may have a thickness of 20 to 50 nm. The metal oxide Ti02The deposition method of the gel film may be as follows: depositing a metal oxide Ti0 on the surface of the paper to be repaired by a surface sol-gel method by taking tetrabutyl titanate as a precursor2And (3) gel films.
According to the invention, the self-assembled composite film of the chitosan and carboxymethyl cellulose layers is obtained by alternately depositing the chitosan lactate assembly layer and the carboxymethyl cellulose sodium salt assembly layer on the surface of the paper to be repaired, and the self-assembled composite film has the following beneficial effects:
(1) the layer-by-layer self-assembly can form an ultrathin film with controllable thickness on almost any surface, and is a widely adopted nano film forming technology. The invention is applied to the reinforcement and restoration of paper documents by adopting a layer-by-layer self-assembly technology for the first time. The color difference of the paper after the reinforcement and repair is not changed, the appearance of the paper is as old as the repair, and the strength and the folding endurance of the paper are obviously improved.
(2) The method can obviously improve the hydrophobic property of the paper, prevent the swelling effect of the invasion of water on the cellulose and reduce the hydrolysis of the cellulose, and the characteristic can reduce the water absorption of the paper cellulose, thereby slowing down the swelling and degradation of the water on the fiber and the damage of hydrogen bonds. In addition, the hydrophobic surface of the paper effectively reduces the attachment of microorganisms, and the chitosan layer inhibits the growth of the microorganisms, so that the condition of damage by worms and corrosion of the paper is reduced. And after the paper is subjected to damp-heat aging and ultraviolet aging treatment, various performance indexes are improved to a great extent compared with those before the treatment.
(3) The method can be used for reinforcing different types of paper with different acidification degrees, has obvious effect of improving the mechanical property, particularly the folding resistance, and has a certain deacidification effect. The writing of the repaired paper is not affected, and the appearance of the paper is not distinguished by visual change. It follows that the invention has general applicability.
(4) In the invention, by adjusting the number of self-assembly layers, the mechanical property, alkalinity and alkali retention of the paper can be optimized and improved.
Drawings
FIG. 1 is a schematic view of the structure of a reactor used in examples.
The device comprises a reaction tank 1, paper to be repaired 2, a porous support plate 3, a temperature control heater 4, a repair liquid discharge port 5, a spray head 6, a spray distribution plate 7, an annular overflow groove 8, a cold trap 9, a vacuum pump 10, a vacuum control system 11, a self-assembly liquid storage tank 12, a peristaltic pump 13, a control valve I14, a cleaning liquid storage tank 15, a peristaltic pump II 16 and a control valve II 17.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The chitosan lactate used in the following examples was a water-soluble salt obtained from Synbiotic manufacturing Co., Ltd, Wuhan City. Sodium carboxymethyl cellulose was purchased from czech biotechnology limited. The preparation process of the shell carboxymethyl cellulose with the pH of 7.5-7.8 and the concentration of 1.0mg/ml is as follows: directly dissolving the raw material with water to obtain the required concentration.
The structure of the 260X 320X 40mm reactor used in the following examples is shown in FIG. 1, and it includes a self-assembly reaction system, a spraying system, a vacuum infiltration system, a sample injection system and a cleaning system;
the self-assembly reaction system is a reaction tank 1, a porous support plate 3 used for placing paper 2 to be repaired is horizontally arranged in the middle of the reaction tank 1, the aperture ratio of the porous support plate is 0.5-1.5%, holes in the porous support plate are uniformly distributed, and the aperture is 0.05-0.1 mm. The reaction tank 1 is provided with a temperature control heater 4 to control the temperature of the reaction tank and provide proper conditions for the self-assembly reaction of the surface of the paper to be repaired. The bottom of the side wall of the reaction tank 1 is also provided with a repairing liquid discharge port 5.
The spraying system is positioned above the porous supporting plate 3 and used for spraying the self-assembly liquid on the paper to be repaired, and comprises a spray head 6, a spraying distribution plate 7 and an annular overflow groove 8, wherein the spraying distribution plate 7 is arranged in parallel with the porous supporting plate 3 so as to uniformly spray the self-assembly liquid on the surface of the paper to be repaired. The annular overflow groove 8 is positioned between the spray distribution plate 7 and the side wall of the reaction tank 1 and is used for collecting redundant self-assembly feed liquid or cleaning liquid.
The vacuum filtration system is connected with the side wall of the reaction tank 1 below the porous support plate 2 and used for enabling the self-assembly liquid to permeate the paper to be repaired and form a film on the surface of the paper to be repaired, and comprises a cold trap 9, a vacuum pump 10 and a vacuum control system 11 which are sequentially connected, wherein the vacuum pump 10 and the vacuum control system 11 provide proper vacuum degree for the space below the porous support plate 3 in the reaction tank 1, and the vacuum degree can be flexibly adjusted according to the type of the paper to be repaired. The cold trap 9 is arranged to facilitate condensation of water vapor and prevent a large amount of water vapor from entering the vacuum pump.
The sample introduction system comprises a self-assembly material liquid storage tank 12, a peristaltic pump I13 and a control valve I14 which are sequentially connected, and the self-assembly material liquid enters the spraying system through the peristaltic pump I13 under the control of the control valve I14 (the conveying speed is controlled); the cleaning system comprises a cleaning liquid storage tank 15, a peristaltic pump II 16 and a control valve II 17 which are sequentially connected, and the cleaning liquid enters the spraying system through the peristaltic pump II 16 under the control of the control valve II 17 (the conveying speed is controlled); and the self-assembly feed liquid and the cleaning liquid alternately enter a spraying system.
For example, when a layer of A/B self-assembled film is assembled on the surface of the paper to be repaired, when the device is used,
firstly, self-assembly feed liquid A in self-assembly feed liquid storage tank 12 is under the control of control valve I14 (control transfer rate), get into spraying system through peristaltic pump I13, through shower nozzle 6 and the surface of the paper 2 of waiting to restore of spraying distribution plate 7 even spraying placing on porous backup pad 3, unnecessary self-assembly feed liquid is collected by annular overflow launder 8, under the effect of vacuum pump 10 and vacuum control system 11 in vacuum filtration system, self-assembly feed liquid A infiltration paper waiting to restore, form rapid draing's rete A:
then, under the control of a control valve II 17 (controlling the conveying speed), the cleaning liquid in the cleaning liquid storage tank 15 enters a spraying system through a peristaltic pump II 16, the operation is repeated, the cleaning liquid permeates the membrane layer A, and the membrane is cleaned;
then, the self-assembly material liquid B repeats the operation to form a film layer B, and the A and the B are self-assembled through hydrogen bonds or electrostatic acting force under the control of the temperature control heater 4 to form a self-assembly film A/B, so that the paper is repaired (the time for forming the A/B self-assembly film can be flexibly controlled by a vacuum system according to different self-assembly materials).
After the repair is completed, the repair liquid is discharged from the repair liquid discharge port 5.
Wherein, each parameter is controlled as follows: the conveying speed of the self-assembly feed liquid is 10-50 mL/min, the pressure of a spray head is 2-5 bar, the spraying time is 5-20 minutes, the temperature of a temperature control heater is controlled at 30 ℃, and the vacuum degree of a vacuum filtration system is controlled at 10 DEG C-2～10-3Pa。
The mechanical properties (tensile strength and folding strength) were measured as follows: the folding endurance of the paper is tested according to ISO 5626:1993 by adopting an NZ-135 folding endurance instrument; the tensile strength of the paper is tested according to ISO 1924-2:2008 by adopting a model KZW-300 micro-control tensile testing machine.
The paper after consolidated repair is tested for pH according to the method described in ISO 6588-1: 2012: a sample (2 g) was extracted with 100mL of cold distilled water for 1 hour, and the pH of the extract was measured at 20 to 25 ℃.
And testing the chroma of the paper before and after repairing by adopting a model NH310 color difference meter.
The artificial damp-heat aging simulation experiment is carried out according to the method of ISO 5630-3:1996, and specifically comprises the following steps: the repaired paper was placed in an oven at 80 ℃ and a relative humidity of 65% for 72 hours. And testing the mechanical property, pH, color difference change and other properties of the aged paper sample, and comparing the mechanical property, pH, color difference change and other properties with the original test result before repair to detect the retention condition of each property.
The ultraviolet light aging simulation experiment is carried out according to the following method: and (3) irradiating the repaired paper for 72 hours at normal temperature by a 16 cm-radius ultraviolet lamp with the wavelength of 260nm and the power of 20W. And testing various performances of the aged paper pattern such as mechanical property, pH, color difference change and the like, and comparing with the original test result before repairing to detect the retention condition of various performances.
EXAMPLE 1 reconditioning paper documents
Taking 200X 280mm acidic machine-made paper (1986), placing the paper in a reactor of 260X 320X 40mm, and adopting chitosan lactate and sodium carboxymethyl cellulose saline solution with the concentration of 1.0mg/ml to alternately carry out layer-by-layer self-assembly deposition to obtain the chitosan and carboxymethyl cellulose layer-by-layer self-assembly composite film (the number of self-assembly layers is one) on the surface of the paper to be repaired. The thickness of the composite membrane is 70nm, in the self-assembly layer, the thickness of the chitosan lactate assembly layer is 35nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 35 nm.
The performance parameter pairs before and after repair by self-assembly of one layer are shown in table 1:
TABLE 1 comparison of Performance parameters of paper before and after one layer self-assembly repair
As can be seen from Table 1, the pH of the paper after one-layer self-assembly repair can reach a slightly alkaline pH value, and the deacidification effect is good. The tensile strength of the paper is improved by 33.31%, the folding endurance is improved by 146.50% (double-folding times), and the mechanical property is obviously improved. There was no visible color difference change.
Example 2 repairing paper document
Taking 200X 280mm acidic machine-made paper (1986), placing the paper in a reactor of 260X 320X 40mm, and adopting aqueous solutions of polysaccharide lactate and sodium carboxymethyl cellulose with the concentrations of 1.0mg/ml to alternately carry out layer-by-layer self-assembly deposition to obtain the chitosan and carboxymethyl cellulose layer-by-layer self-assembly composite membrane (the number of self-assembly layers is two) on the surface of the paper to be repaired. The thickness of the composite membrane is 140nm, in each self-assembly layer, the thickness of the chitosan lactate assembly layer is 70nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 70 nm.
The performance parameter pairs before and after repair by bilayer self-assembly are shown in table 2:
TABLE 2 comparison of Performance parameters of paper before and after two-layer self-assembly repair
As can be seen from Table 2, the pH of the paper after the two-layer self-assembly repairing can reach a slightly alkaline pH value, and the deacidification effect is good. The tensile strength of the paper is improved by 88.64%, the folding endurance is improved by 151.49% (double-folding times), and the mechanical property is obviously improved. There was no visible color difference change.
Example 3 repairing paper document
Cutting 200 × 280mm Beijing Japanese newspaper (1978) into pieces, placing in a reactor of 260 × 320 × 40mm, using tetrabutyl titanate as precursor, and depositing ultrathin metal oxide Ti0 on the surface of paper by surface sol-gel method2The gel film (the film thickness is 20-50 nm) is specifically operated as follows: dissolving 13.6 ml (0.1mol/L) of tetrabutyl titanate in 400 ml of isopropanol solution, slowly passing 200 ml of the solution through the paper sample to be repaired by controlling the vacuum degree, keeping the rest 200 ml of the solution on the paper to be repaired for 3 minutes, quickly filtering, and washing off the metal alkoxide remained on the surface of the paper to be repaired by using a large amount of ethanol. And then adding 400 ml of deionized water to the surface of the paper to be repaired, standing for 3 minutes until the titanium alkoxide is hydrolyzed and forms a gel layer, then washing with a large amount of ethanol through suction filtration, drying at atmospheric temperature, and finally forming an ultrathin titanium dioxide gel layer on the surface of the paper to be repaired.
And then, adopting glycan lactate with the concentration of 1.0mg/ml and sodium carboxymethyl cellulose saline solution to alternately carry out layer-by-layer self-assembly deposition, and obtaining the titanium dioxide modified chitosan and carboxymethyl cellulose layer-by-layer self-assembly composite membrane (the number of self-assembly layers is one) on the surface of the paper to be repaired. The thickness of the composite film is 100nm, and each self-assembly layer contains Ti02The thickness of the gel film can be 30nm, the thickness of the chitosan lactate assembly layer is 35nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 35 nm.
The performance parameter pairs before and after repair by self-assembly of one layer are shown in table 3:
TABLE 3 comparison of Performance parameters of paper before and after one layer of self-assembled repair
As shown in Table 3, the alloy passes through Ti02After modification, the pH value of the paper can reach partial alkalinity after a layer of self-assembled film is assembled, and the deacidification effect is good. The tensile strength of the paper is improved by 78.79%, the folding endurance is improved by 251.30% (double-folding times), and the mechanical property is obviously improved. There was no visible color difference change.
Example 4 repairing paper document
Cutting 200 × 280mm Beijing Japanese newspaper (1978) into pieces, placing in a reactor of 260 × 320 × 40mm, using tetrabutyl titanate as precursor, and depositing ultrathin metal oxide Ti0 on the surface of paper by surface sol-gel method2And (3) alternately carrying out layer-by-layer self-assembly deposition on the gel film (the specific operation is the same as that in the example 3), and then, obtaining the titanium dioxide modified chitosan and carboxymethyl cellulose layer-by-layer self-assembly composite film (the number of self-assembly layers is two) on the surface of the paper to be repaired. The thickness of the composite film is 170nm and Ti02The thickness of the gel film can be 30nm, in each self-assembly layer, the thickness of the chitosan lactate assembly layer is 35nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 35 nm.
The performance parameter pairs before and after repair by two-layer self-assembly are shown in table 4:
TABLE 4 comparison of Performance parameters of paper before and after two-layer self-assembly repair
As shown in Table 4, the product was Ti02After modification, the pH value of the paper can reach partial alkalinity after the two layers of self-assembled films are assembled, and the deacidification effect is good. The tensile strength of the paper is improved by 95.45%, the folding endurance is improved by 334.72% (double-folding times), and the mechanical property is obviously improved. There was no visible color difference change.
Example 5 repairing paper document
Cutting 200 × 280mm BeijingOne daily newspaper (1978) is placed in a reactor of 260X 320X 40mm, tetrabutyl titanate is used as a precursor, and ultrathin metal oxide Ti0 is deposited on the surface of paper by a surface sol-gel method2And (3) alternately carrying out layer-by-layer self-assembly deposition on the gel film (the specific operation is the same as that in the example 3), and then, obtaining the titanium dioxide modified chitosan and carboxymethyl cellulose layer-by-layer self-assembly composite film (the number of self-assembly layers is three) on the surface of the paper to be repaired. The thickness of the composite film is 240nm, wherein, Ti02The thickness of the gel film can be 30nm, in each self-assembly layer, the thickness of the chitosan lactate assembly layer is 35nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 35 nm.
The performance parameter pairs before and after repair by three-layer self-assembly are shown in table 5:
TABLE 5 comparison of Performance parameters of paper before and after three-layer self-assembly repair
As shown in Table 5, the alloy passes through Ti02After modification, the pH value of the paper can reach partial alkalinity after the three-layer self-assembled film is assembled, and the deacidification effect is good. The tensile strength of the paper is improved by 109.09%, the folding endurance is improved by 462.95% (double-folding times), and the mechanical property is obviously improved. There was no visible color difference change.
Artificial damp-heat aging simulation experiment for paper documents repaired in embodiment 6 and embodiment 3
The base paper pattern and the titanium dioxide pre-modified self-assembled repair paper pattern of example 3 were placed in an oven at 80 ℃ and a relative humidity of 65% for 72 hours. And testing various performances of the aged paper sample such as mechanical property, pH, color difference change and the like, and comparing with the original test result before repairing. As shown in Table 6, the tensile strength of the single-layer self-assembly repair paper sample after aging is improved by 214.26% compared with the tensile strength of the base paper sample after aging, the folding resistance is improved by 113.55%, and the mechanical property is obviously improved.
TABLE 6 comparison of Performance parameters before and after Damp-Heat aging of paper before and after repair of Single-layer self-assembled film
Artificial damp-heat aging simulation experiment for paper documents repaired in example 7 and example 4
The base paper pattern of example 4 and the self-assembled repair paper pattern pre-modified with titanium dioxide were placed in an oven at 80 ℃ and a relative humidity of 65% for 72 hours. And testing various performances of the aged paper sample such as mechanical property, pH, color difference change and the like, and comparing with the original test result before repairing. As shown in Table 7, the tensile strength of the double-layer self-assembly repair paper sample after aging is improved by 67.53 percent compared with that of the base paper sample after aging, the folding resistance is improved by-6.54 percent, and the mechanical property is obviously improved.
TABLE 7 comparison of Performance parameters before and after Damp-Heat aging of paper before and after repair of double-layer self-assembled film
Artificial damp-heat aging simulation experiment for paper documents repaired in example 8 and example 5
The base paper pattern of example 5 and the self-assembled repair paper pattern pre-modified with titanium dioxide were placed in an oven at 80 ℃ and a relative humidity of 65% for 72 hours. And testing various performances of the aged paper sample such as mechanical property, pH, color difference change and the like, and comparing with the original test result before repairing. As shown in Table 8, the tensile strength of the three-layer self-assembly repair paper sample after aging is improved by 84.42% compared with that of the base paper sample after aging, the folding resistance is improved by 20.09%, and the mechanical property is obviously improved.
TABLE 8 comparison of Performance parameters before and after Damp-Heat aging of paper before and after repair of three layers of self-assembled films
Ultraviolet light aging simulation experiment of paper documents repaired in examples 9 and 5
The original paper pattern of example 5 and the self-assembled repair paper pattern pre-modified with titanium dioxide were irradiated at room temperature with an ultraviolet lamp of 16cm radius, a wavelength of 260nm, and a power of 20W for 72 hours. And testing the mechanical property of the paper pattern after ultraviolet aging, and comparing the mechanical property with the original test result before repairing. As shown in Table 9, the tensile strength of the self-assembled repaired paper sample after ultraviolet aging is improved by 35.04 percent compared with that of the base paper sample after ultraviolet aging, the folding resistance is improved by 125 percent, and the mechanical property is obviously improved.
TABLE 9 comparison of Performance parameters before and after UV aging of paper before and after repair of three-layer self-assembled film
Claims (8)
1. A method of repairing a paper document, comprising: the method utilizes a layer-by-layer self-assembly film forming technology to form a film on the surface of the paper to be repaired, so as to realize paper repair;
the method comprises the following steps: alternately depositing a water-soluble chitosan assembly layer and a carboxymethyl cellulose sodium salt assembly layer on the surface of the paper to be repaired to obtain a self-assembly composite film of the water-soluble chitosan and the carboxymethyl cellulose layer;
the thickness of the self-assembled composite film of the water-soluble chitosan and the carboxymethyl cellulose layer is 50-400 nm; the number of self-assembly layers of the water-soluble chitosan and carboxymethyl cellulose layer self-assembly composite film is 1-10; in each self-assembly layer, the thickness of the water-soluble chitosan assembly layer is 30-80 nm, and the thickness of the sodium carboxymethyl cellulose assembly layer is 30-80 nm.
2. The method of claim 1, wherein: the film forming method is characterized in that a film forming material permeates on the surface of the paper to be repaired by a vacuum permeation method.
3. The method of claim 2, wherein: the steps of the vacuum infiltration method are as follows: and laying the paper to be repaired on the porous support plate, and alternately performing controllable vacuum filtration on the water solution of the water-soluble chitosan and the water solution of the sodium carboxymethyl cellulose.
4. The method of claim 3, wherein: the concentrations of the water solution of the water-soluble chitosan and the water solution of the sodium carboxymethyl cellulose are both 0.8-1.5 mg/mL; and/or the aperture ratio of the porous support plate is 0.5-1.5%, the pores are uniformly distributed on the porous support plate, and the pore diameter is 0.05-0.1 mm.
5. The method according to any one of claims 2-4, wherein: the vacuum infiltration adopts the following devices: the device comprises a spraying system, a self-assembly reaction system and a vacuum filtration system; the self-assembly reaction system is a reaction tank, and a porous support plate for placing paper to be repaired is horizontally arranged on the reaction tank; the spraying system is positioned above the porous supporting plate and is used for spraying self-assembly feed liquid on the paper to be repaired; and the vacuum filtration system is connected with the side wall of the reaction tank below the porous support plate and is used for enabling the self-assembly liquid to permeate the paper to be repaired, forming a film on the surface of the paper to be repaired and drying the film.
6. The method of claim 5, wherein: the device also comprises a cleaning system for cleaning the membrane, the cleaning system is connected with the spraying system, cleaning liquid in the cleaning system is sprayed on the surface of the membrane of the paper to be repaired through the spraying system, and the cleaning liquid permeates the membrane under the action of the vacuum filtration system, namely the membrane is cleaned.
7. The method according to any one of claims 1-4, wherein: the alternate deposition is preceded by the step of depositing a layer of metal oxide Ti0 on the surface of the paper to be repaired2And (5) gel film forming.
8. The method of claim 7, wherein: the metal oxide Ti02The thickness of the gel film is 20-50 nm.
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| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
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| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
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