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2016Year35volume8Expect CHEMICAL INDUSTRY AND ENGINEERING PROGRESS ·2507·

research and develop

Self-healing properties of polyvinyl alcohol hydrogel

Gong Guisheng, Liu Jingbo, Zhong Yupeng, Lin Qiang, Zhang Faai

(School of Materials Science and Engineering, Guilin University of Technology, Guilin, Guangxi541004)

Summary:High concentration polyvinyl alcohol (PVA) hydrogel has a certain repairing function, but the research on its self-repairing mechanism and the influence of preparation process

parameters on its repairing performance is lacking. In this paper, high-concentration self-healingPVAHydrogel, adjusted byPVAHydrogel preparation process parameters (PVA Molecular

weight,PVAConcentration, freezing time, thawing time, freezing-thawing times, repairing time, freezing temperature, etc.) to obtain the optimal process conditions, analyze the hydrogel self-

repairing mechanism, and studyPVAMultiple self-healing properties of hydrogels. The research results show that: the relative molecular massPVAThe prepared hydrogel has good self-healing

performance; the freezing time is2 hours, the unfreezing time is1h, the hydrogel prepared by one freeze-thaw cycle has the best self-repair performance, and the best repair time is12 hours,

which can better carry out repeated self-repair. It is pointed out that the self-healing performance of hydrogel is mainly formed by the interaction of reversible hydrogen bonds inside it, and

its main influence comes from the content of hydroxyl groups inside the hydrogel and thePVAmolecular mobility. Key words:polyvinyl alcohol; self-healing; hydrogel; preparation;

mechanism CLC number:O 643

Document identification code:A Article ID:1000‒6613(2016)08‒2507‒06

DOI:10.16085/j.issn.1000-6613.2016.08.31

Self-healing performance of poly(vinyl alcohol) hydrogel

GONG Guisheng,LIU Jingbo,ZHONG Yupeng,LIN Qiang,ZHANG Faai

(College of Materials Science and Engineering,Guilin University of Technology,Guilin 541004,Guangxi,China)

Abstract:The high concentration of poly(vinyl alcohol) hydrogels possesses self-healing property.

However,its self-healing mechanism and the effects of the preparation conditions on the self-healing
property of the hydrogel were rarely studied.,The high concentration PVA hydrogel was prepared by the
freezing and thawing method. The optimum conditions were obtained by changing the preparation
conditions(the PVA molecular weight,PVA concentration,freezing time,thawing time, numbers of freezing
and thawing cycles,healing time,freezing temperature,etc.)and the self-healing mechanism was analyzed.
The multiple self-healing performance of the hydrogel was also investigated. The results showed that the
larger the molecular weight of the PVA,the better the self-healing performance of the hydrogels. The
hydrogels prepared under 2h freezing and 1h thawing in only one cycle showed the best self-healing
performance,and the best healing time was 12h. The PVA hydrogel could self-heal for many times. The self-
healing property of the hydrogel was due to the interaction of reversible hydrogen bond,which was mainly
influenced by the content of hydroxyl group and the mobility of the PVA molecules in the hydrogel.

Key words:poly (vingl alcohol)(PVA);self-healing;hydrogels;preparation;mechanism

Materials are always affected by some external factors during use

The impact will cause a certain degree of damage to the material, and this slight damage Received date:2015-11-12;Date of revision:2015-12-29. Fund

Injury will affect the normal use of the material, and will also lead to waste of the material project:National Natural Science Foundation of China (51263004

). First author:Gong Guisheng (1990—)

, male, postgraduate.Contact:Faai Zhang, teach
fee. Therefore, materials with self-healing functional properties emerge as the times require.
Professor, doctoral supervisor, mainly engaged in the research of polymer nanocomposites, natural

The self-healing function means that when an object is damaged by the outside world, it can product chemistry, and self-healing polymers.E-mail zhangfaai@163.com.
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Ability to self-heal incisions[1]. Through the self-repair function, the service life of the Experimental Machine Manufacturing Co., Ltd.WDW-20Microcomputer controlled

material can be extended, and the maintenance work can be greatly reduced. electronic universal testing machine for tensile test, tensile rate100mm/min, the

Effort and cost purposes[2-4]. Therefore, materials with self-healing properties have test temperature is25℃.

always been one of the research hotspots.[5-7]. The repair rate uses the formula (1)Calculation.

Physical polyvinyl alcohol (PVA) hydrogel meansPVAPhysically δ

repair rate =1x100% (1)
cross-linked after repeated freezing-thawing process after dissolution δ0
A gel that stabilizes the network structure. The gel has a high water content, mechanical In the formula,δ0andδ1are the fracture stresses before and after hydrogel self-healing,

The advantages of high strength, non-toxicity and good biocompatibility have caused many respectively.

researcher's attention[8-10], has been widely used in biomedicine, wastewater treatment, (3) Determination of the gel fraction of hydrogel samples in

artificial articular cartilage and other fields[11-14]. because PVAThe hydrogel contains a large 60Dry to constant weight at ℃W1. then in60℃ Soak in deionized

number of hydroxyl groups, making high concentrationPVAHydrogel has very excellent water4 day, remove the uncrosslinkedPVAmolecular. hydrogel

characteristics - self-healing function[15]. Various experimental conditions, such asPVA samples60°C dried to constant weightW2.PVAThe gel ratio of

Molecular weight, freezing time, thawing time, freezing temperature, multiple self-repairing, (2)calculated[16].
etc.PVAThe influence of self-healing properties of hydrogels is rarely reported in the W (2)
Gel rate =2x100%
literature. W1
In this paper, different relative molecular masses were usedPVAresin preparation
2Results and discussion
high concentrationPVAhydrogels, their self-healing properties were studied, and

on this basis, the effects ofPVAFactors in the self-healing properties of hydrogels, 2.1Self-healing process and its mechanism

find out the optimal conditions for preparing self-healing hydrogels, and picture1for physical crosslinkingPVASchematic diagram of the internal cross-linking structure of the

rightPVAThe self-healing mechanism of self-healing hydrogels was explored for self- hydrogel. D1It can be seen that the physically cross-linked hydrogel prepared by freeze-thaw treatment is

healingPVAThe practical application of hydrogel provides a reference. divided into two parts for cross-linking: ① freeze-thaw process, PVAA microcrystalline structure is formed

between the molecules, and these microcrystals are used as cross-linking points to form a gel. This type of
1Experimental part
cross-linking is irreversible[17]; ② After thawing, a large number of uncrosslinked hydroxyl groups inside the

1.1Experimental material hydrogel can interact with each other through hydrogen bonds.

polyvinyl alcoholPVA-124(degree of alcoholysis98%~99%), m Cross-linking, such cross-linking is reversible cross-linking. The second type of crosslink is

no=105000,AR, Shantou Xilong Chemical Co., Ltd.; polyvinyl alcohol PVAHydrogels are the basis for self-healing.

PVA-117(degree of alcoholysis98%~99%) ,mno=79000, picture2forPVADiagram of the self-healing process of hydrogels. In order to verify

AR, Aladdin (Shanghai) Co., Ltd. the self-healing performance of the hydrogel, two hydrogel samples were prepared: the

1.2 PVAPreparation of hydrogel One is the original hydrogel sample, the other is rhodamineBStained

Preparation of physically cross-linked self-healing materials by freeze-thaw hydrogel samples. Cut the original hydrogel into two parts with scissors (1) ,
methodPVAHydrogels. The preparation method is as follows: a certain quality ofPVA Then the two samples were bonded on the fracture surface (2), until the

Add the resin and distilled water into the three-necked flask,95at ℃25r/minrate sample self-repair24hAfterwards, rhodamine in the hydrogelBable to

stirring1h, made into a solution of specified concentration. treatPVAAfter everything interpenetrate (3)test was carried out on a universal tensile testing machine (4) ,Sample
, the tensile

is dissolved, pour it into the ideal mold in ‒25℃ freezer freezer2 hoursshape, then

thaw at room temperature1h, so that for a freeze-thaw cycle, different freeze-thaw

times were preparedPVAHydrogels.

1.3Performance Testing

(1) morphology observation preparationPVAAfter the hydrogel, the sample was

cut with scissors, and then manually glued at the incision, and the sample was in

Repair at room temperature24hFinally, a digital camera was used to take pictures of the samples before and

after restoration.

(2) mechanical property characterizationPVAhydrogel cut80.0mm x6.0x

3.5mmThe left and right experimental splines are cut and self-repaired, and the

before and after repairPVAHydrogel samples were obtained from Hunan Tianchen picture1PVASchematic diagram of internal crosslinking of hydrogel
No.8Expect Gong Guisheng et al.: Self-healing properties of polyvinyl alcohol hydrogel ·2509·

picture2PVAPhoto of hydrogel self-healing process

product breaks at the wound (5). From the tensile results, it can be seen that the hydrogel

breaks after reaching a large deformation, indicating that the hydrogel has a good

self-healing effect.

2.2self-healing performance

2.2.1 PVAThe effect of relative molecular mass

The quality score is30%ofPVA-124andPVA-117The aqueous solution goes

through ‒25℃ freezing2 hours, thawed at room temperature1hA freeze-thaw

treatment produced hydrogels. picture3forPVAEffect of relative molecular mass on

self-healing properties of hydrogels. It can be seen from the figure that under the
picture4 Effect of Concentration on Gelation Rate and Self-healing Properties of Hydrogels

same freezing time, the low relative molecular massPVA-117higher relative

molecular massPVA-124The original tensile strength of the hydrogel is large, but Freeze-thaw treatments produced hydrogels. picture4(a)forPVAThe effect of concentration on the

PVA-117The self-healing efficiency of the hydrogel (48%) is lower than the relative gelation rate of hydrogels. It can be seen that as the concentration increases, the gel fraction

molecular massPVA-124self-healing efficiency (80%) . This is because increases, indicating thatPVAThe degree of internal cross-linking of the hydrogel increases. picture

low molecular massPVAThe molecular chain is relatively short, and it is easy to contact between the molecular chains under 4(b)forPVAThe effect of concentration on the self-healing properties of hydrogels. prepared under the

freezing conditions. After freezing-thawing treatment, it is easy to form a microcrystalline structure between the molecular same conditionsPVAHydrogels,PVAThe higher the concentration of the aqueous solution, the greater

chains and improve the tensile strength. An increase in the degree of crosslinking inside the hydrogel will lead to a decrease the original tensile strength of the hydrogel. This is because with the solution

in the uncrosslinked hydroxyl groups, so the strength of the hydrogel to perform hydrogen bond self-repair through the Concentration increase, per unit volumePVAAs the number of molecules increases, the number of condensation points

uncrosslinked hydroxyl groups decreases. forming interchain hydrogen bonds increases. At the same time, the crystallinity of the gel also increases with the

2.2.2 PVAEffect of Concentration The concentration increased significantly, resulting in the strength of the gel with the concentration

The quality scores are25%,30%,35%ofPVA-124 enhance and enhance[18]. However, the tensile strength of the hydrogel repaired increases with the

The aqueous solution goes through ‒25℃ freezing3 hours, thawed at room temperature1ha cold mass fraction from25%arrive35%There is a trend of first increasing and then decreasing. This is

because: on the one hand, when the hydrogel concentration is too low, there is no

Less cross-linked hydroxyl groups are not conducive to the self-healing of hydrogels; the other side

On the other hand, when the concentration of the hydrogel is too high, its molecular fluidity will decrease, and it will not

Facilitate the formation of hydrogen bond interactions between uncrosslinked hydroxyl groups. therefore,

whenPVAquality score is30%, the hydrogel not only ensures the number of uncrosslinked

hydroxyl groups in the molecule, but also has sufficient fluidity to ensure

Hydrogels are capable of self-healing through uncrosslinked hydroxyl groups. so when concentrated

degree is30%hour,PVAThe tensile strength of the hydrogel reaches the initial

strength after self-healing54%.

2.2.3The effect of freezing time

picture3Effect of Relative Molecular Mass on Self-healing Properties of Hydrogels The quality score is30%ofPVA-124aqueous solution in
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‒ 25Separately freeze at ℃2 hours,3 hours,4h, thawed at room temperature

1hA freeze-thaw treatment produced hydrogels. D5(a)It can be seen that the

gel rate of the hydrogel increases with the increase of freezing time.

improve. This is due to the freezing process to allowPVAThe molecular motion

state of the aqueous solution is "frozen" at a certain moment, making each other

The contacted molecular chains can interact to form microcrystalline cross-linking points, so

The freezing time is increased, the internal cross-linked structure of the hydrogel is tight, and the gel

rate increased. picture5(b)for freezing timePVA-124The effect of hydrogel self-healing

properties. It was found that with freezing time from2 hoursarrive4h, the self-healing

efficiency of the hydrogel from80%Lowered to40%. This is because as the freezing time
picture6 Effect of thawing time on the self-healing performance of hydrogel

increases, the irreversible microcrystalline cross-linking inside the hydrogel increases

High, so the tensile strength gradually increases. However, due to freezing time The joint part is the same, but with the increase of thawing time, the hydrogel

Prolonged, the reversible cross-linked hydroxyl groups inside the gel are reduced, which is not conducive to hydrogel The partially uncrosslinked hydroxyl groups gradually crosslink each other through hydrogen bonds, resulting in hydraulic coagulation.

Self-healing through reversible hydrogen bonds between hydroxyl groups, self-healing tensile strength The internal structure of the gel is more stable, and the free water inside the hydrogel volatilizes

The degree is reduced, and the self-healing efficiency is reduced. hair, the molecular fluidity decreases, which leads to the initial stretching of the hydrogel

Increased strength. And with the prolongation of thawing time, the hydrogel self-healing

After the tensile strength is basically unchanged, this is due to the

Except for the hydroxyl group of the reversible cross-linking part, with the extension of time, the hydrogel

The number of hydroxyl groups reversibly cross-linked by internal hydrogen bonds does not change, and the self-healing is strong

The degree changes little.

2.2.5Influence of freeze-thaw times

The quality score is30%ofPVA-124aqueous solution through the

‒ 25Freeze at ℃2 hours, thawed at room temperature1hof1Second-rate,2Second-rate,3The hydrogels

were prepared by repeated freeze-thaw cycles. picture7(a)is the number of freeze-thaw pairsPVA-124

Effect of hydrogel gel fraction. It can be seen that as the number of freezing-thawing changes from1

times increased to3Second, the gel fraction of the hydrogel ranges from69%improve to80%. This is

due to the increase in the number of freeze-thaws, the gel insidePVAThe degree of cross-linking of the

molecules through the crystallite increases, and the network structure of the gel becomes tighter, so

the gel rate is greatly improved. from

picture7(b)The tensile test results before and after hydrogel repair can also be seen, with the increase

of freezing-thawing times,PVAThe tensile strength of the hydrogel is greatly improved. When the

number of freeze-thaw cycles increases,PVAThe inter-chain and intra-chain hydroxyl groups in the gel

form an increase in the number of microcrystals, and the stability between crystal grains

The properties are also significantly improved, and the network structure of the gel is tighter, which leads to

The tensile strength of the gels increases with the number of freeze-thaw cycles. In

contrast, hydrogen-bonded reversibly cross-linked hydroxyl groups inside hydrogels

picture5Effects of Freezing Time on the Gelation Rate and Self-healing Properties of Hydrogels
The increase of freezing-thawing times greatly reduces the number of reversible

hydrogen bonds in hydrogel self-healing, so the strength after repairing decreases.

2.2.4Effect of thaw time low, the self-healing efficiency of the hydrogel ranges from81%decrease to2%.

The quality score is30%ofPVA-124aqueous solution in 2.2.6The impact of repair time

‒ 25Freeze at ℃2 hours, thawed at room temperature1h,6 hours,12 hours,24h A freeze-thaw The quality score is30%ofPVA-124Aqueous solution through

treatment produced hydrogels. by figure6It can be seen that the initial strength of the ‒ 25℃ freezing2 hours, thawed at room temperature1hA freeze-thaw treatment produced

hydrogel increases with the increase of thawing time. Under the condition of the same hydrogels. D8repair time pairPVA-124The effect of hydrogel self-healing properties can be

freezing time, the irreversible crystallite exchange inside the hydrogel seen from the results, as the self-healing properties of the hydrogel
No.8Expect Gong Guisheng et al.: Self-healing properties of polyvinyl alcohol hydrogel ·2511·

picture9Effect of freezing temperature on the self-healing properties of hydrogels

hydrogels with the same elongation. picture9for the freezing temperaturePVAThe effect of

hydrogel self-healing properties. D9It can be seen that as the freezing temperature

decreases, the tensile strength of the repaired hydrogel increases, and the repaired

The recovery efficiency is improved. This is when the freezing temperature is high and the freezing time is too long

will causePVAEvaporation of free water in hydrogel[19], resulting in a decrease in the molecular flow

inside the hydrogel, which is not conducive to the hydrogel passing through the hydroxyl

Self-healing is performed, and self-healing performance is degraded. And the freezing temperature is

‒ 25°C, the freezing time is shorter, so the obtainedPVAThe hydrogel has a higher water

content and better molecular fluidity, which is conducive to the passage of the hydrogel

Uncrosslinked hydroxyl groups in the internal molecular chain form reversible hydrogen bonds for self-repair
picture7 Effects of freezing-thawing times on the gelation rate and self-healing properties of hydrogels
complex, so the strength after repair is higher.

2.2.8multiple self-healing

Set the quality score to30%ofPVA-124Aqueous solution in ‒25℃ freezing2

hours, thawed at room temperature1hA freeze-thaw treatment produced

hydrogels. then toPVAThe hydrogel was subjected to repeated repair tests, and the

repeated repair times were10min,30minand60min, the result is shown in the figure

10shown. D10It can be seen from the3In the case of the first1 The tensile strength

after self-healing is relatively high, Repair efficiency reaches25%,

30%and35%, this is because it is the first repair, the hydrogel fracture surface has more free

hydroxyl groups, and the molecular fluidity of the fresh fracture surface is relatively low.

Good; and the subsequent repair efficiency increases with the number of repeated repairs

increase and decrease, when the hydrogel undergoes the first5When self-healing for the first time, its
picture8Effect of repair time on self-healing performance of hydrogel

The repair time is extended, the self-repair efficiency of the hydrogel is improved,12 hours self-

healing efficiency reaches80%. This is due to the extension of the self-healing time, and there is

sufficient time for the hydroxyl groups of the hydrogel molecular chains to contact each other.

and form hydrogen bonds.

2.2.7The effect of freezing temperature

freezing temperature vs.PVAPhysical properties and mechanics of hydrogels

can have a greater impact, therefore,

Freezing temperature also affects self-healingPVA

Important factors for hydrogel preparation. Set the concentration to30%ofPVA-124

The aqueous solution is passed through ‒25℃, ‒18℃, ‒10℃ freezing4h,5h, 10h,

thawed at room temperature1hOne freeze-thaw treatment to prepare the initial pull picture10 Repeated self-healing performance of hydrogel
·2512· change
The fracture surface loses its self-healing ability. This is due to the fracture surface molecular flow
caused by sexual decline. Furthermore, from Fig.10It can also be seen that as the repair
interval increases, the number of repeated repairs decreases, which is due to
Because the repair time is too long, the molecular flow in the hydrogel wound after multiple repairs
Mobility decreases, resulting in reduced tensile strength after self-healing. because
this,PVA-124Hydrogels have good repeated self-healing properties.
3in conclusion
(1) prepared a self-healingPVAHydrogel, the use of relatively
large molecular weightPVA-124The mass fraction obtained for the
raw material preparation is30%ofPVAHydrogels have good self-
healing ability.
(2)High concentrationPVAThe aqueous solution passes through-25Freeze
at ℃2 hours, then thaw at room temperature1hHydrogel repair obtained by one
freeze-thaw cycle12 hours, which has the best self-healing performance.
(3)PVASelf-healing hydrogels have a good ability to repair multiple
times.
references
[1]Li Sichao, Han Peng, Xu Huaping. Self-healing polymer materials[J]．advances in chemistry,2012
, twenty four(7):1346-1352．
[2]Dong Kun, Wei Zhao, Zhi Mao, etc. Self-healing gels: structures, properties and prospects[J]．
Chinese Science (Chemistry),2012,42(6) :741-756．
[3] CAI Z,ZHANG JT,XUE F,et al．2D photonic crystal protein hydrogel
coulometer for sensing serum albumin ligand binding[J]．
Analytical Chemistry,2014,86(10):4840-4847.
[4] ZHANG L,wxya,SUN N,et al．A novel self-healing poly(amic acid)
ammonium salt hydrogel with temperature-responsivity and robust
mechanical properties[J]．Journal of Materials Chemistry A, 2014,2(
twenty one) :7666-7668．
[5] CAI Z,KWAK DH,PUNIHAOLE D,et al．A photonic crystal protein
hydrogel sensor for candida albicans[J]．Angewandte Chemie
International Edition,2015,54(44) :13036-13040．
[6]Li Haiyan, Zhang Libing, Li Jie, etc. Research progress of foreign aid self-healing polymer materials
work Enter exhibition 2016Year35roll
[J]．chemical progress,2014,33(1):133-139,164．
[7]Lei Xinyu, Li Xiaoke, Yu Xiaorong, et al. Research on performance evaluation method of self-healing cement for well
cementing[J].J]．Advances in fine petrochemicals,2015(2) :9-11．
[8] PEPPAS NA,STAUFFER SR．Reinforced uncrosslinked poly(vinyl
alcohol)gels produced by cyclic freezing-thawing processes:a
short review[J]．Journal of Controlled Release,1991,16(3)
:305-310．
[9] LOZINSKY VI,DOMOTENKO LV,ZUBOV AL,et al．Study of
cryostructure of polymer systems.Ⅻ.Poly(vinyl alcohol) cryogels:
influence of low-molecular electrolytes[J]．Journal of Applied
Polymer Science,1996,61(11),1991-1998．
[10] YOKOYAMA F,MASADA I,SHIMAMURA K,et al．Morphology and
structure of highly elastic poly(vinyl alcohol) hydrogel prepared
by repeated freezing and melting[J]．Colloid and Polymer
Science, 1986,264(7):595-601．
[11]Li Fan, Zhang Jinlong, Yin Yuji. Research progress of biomedical high-strength hydrogels[J]．
chemical progress,2012,31(11) :2511-2519,2534．
[12] LI Xinming,CUI Yingde. Sudy on synthesis and chloramphenicol release
of poly(2-hydroxyethylmeth acrylate-co-acrylamide)hydrogels. [J]．
Chinese Journal of Chemical Engineering,2008,16(4) :640-645．
[13] LOZINSKY VI,PLIEVA FM．Poly(vinyl alcohol) cryogels employed as
matrices for cell immobilization．3．Overview of recent research and
developments[J]．Enzyme and Microbial Technology, 1998,twenty
three(3/4) ,227-242．
[14] ZHOU L,HE B,ZHANG F．Facile one-pot synthesis of iron oxide
nanoparticles cross-linked magnetic poly(vinyl alcohol) gel beads for
drug delivery[J]．ACS Applied Materials & Interfaces,2011,4(1) :
192-199．
[15] ZHANG HJ,XIA HS,ZHAO Y．Poly(vinyl alcohol) hydrogel can
autonomously self-heal[J]．ACS Macro Letters,2012,1(11):
1233-1236．
[16] GONZALEZ JS,HOPPE CE,MURACA D,et al．Synthesis and
characterization of PVA ferrogels obtained through a one-pot
freezing-thawing procedure[J]．Colloid and Polymer Science,
2011, 289(17/18)
:1839-1846．
[17]Huang Mei. Study on Polyvinyl Alcohol Gel System by Freezing and Thawing Method[D].Suzhou: Soochow University,2012．
[18]Pan Yusong, Xiong Dangsheng, Chen Xiaolin. Preparation and properties of polyvinyl alcohol hydrogel[J]．
:228-231．
Polymer Materials Science and Engineering,2007(6)
[19]Chen Liqi, Zhang Dekun, Zhang Jinsong, etc. Effect of freezing temperature on properties of polyvinyl
alcohol hydrogels[J]．Tissue Engineering Research and Clinical Rehabilitation in China,2007,11(48):
9679-9682．