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Polyelectrolytes Multilayering of Fillers for Strength Improvement of Filled Paper and Their Functionality
충전지 강도 향상과 기능성 부여를 위한 충전물의 고분자전해질 다층 흡착 처리 기술

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dc.contributor.advisor윤혜정-
dc.contributor.author이제곤-
dc.date.accessioned2017-07-13T17:43:46Z-
dc.date.available2018-01-23-
dc.date.issued2017-02-
dc.identifier.other000000140921-
dc.identifier.urihttps://hdl.handle.net/10371/121085-
dc.description학위논문 (박사)-- 서울대학교 대학원 : 산림과학부, 2017. 2. 윤혜정.-
dc.description.abstract무기 입자 충전물은 제지분야에서 인쇄용지나 백상지 제조에 사용되는 가장 중요한 원료 중 하나이다. 충전물의 적용은 종이의 강도를 감소시키나, 종이의 광학적 특성, 평활성, 인쇄적성 등을 향상시킬 수 있으며 건조에너지와 종이 제조 원가를 줄일 수 있다. 따라서, 종이의 강도 감소를 최소화하면서 충전물 함량을 늘릴 수 있는 충전물 하이로딩 기술에 대한 연구가 필요한 실정이다. 본 연구에서는 충전물 하이로딩을 위한 고분자전해질 다층박막 형성 (Polyelectrolytes multilayering, PEM) 기술 적용 가능성에 대한 탐색과 더불어 고충전지의 강도 향상 기작에 대해 구명하고, 실제 제지 산업에 적용 가능한 PEM 방안과 PEM기술을 이용한 항균성 적용 방안에 대해서 제시하고자 하였다.
고충전지에 적합한 PEM전략을 수립하고, 다층흡착기술에 따른 고충전지 강도 향상 기작을 구명하고자 하였다. 펄프 섬유 또는 충전물에 대한 다층박막 형성은 둘 다 종이의 강도를 향상시킬 수 있었으나, 강도 향상에 대한 효과는 충전물 함량에 따라 달랐다. 펄프 섬유에 대한 다층박막 형성은 충전물 함량이 낮은 조건에서 강도 향상에 더 효과적이었으며, 충전물 함량이 높아질수록 강도 향상 정도는 미비하였다. 반대로 충전물에 대한 다층박막 형성은 충전물 함량이 높은 종이의 강도를 향상시키는 데에 더 효과적이었다. 이는 모델합지의 박리강도 측정을 통한 충전물과 섬유간 결합력 평가와 충전물로만 구성된 필름의 파괴강도 측정을 통한 충전물간 결합력 평가를 통해 충전물 표면에 형성된 다층박막에 의해 충전물과 섬유간, 충전물간 결합력이 증가하여 고충전 종이의 강도가 향상된 것으로 밝혀졌다.
충전물 표면에 형성된 다층박막의 특성과 충전물의 종류가 종이의 강도 향상에 미치는 영향에 대해서 살펴보고자 하였다. 농도가 높아질수록 PDADMAC과 PSS의 흡착량을 향상시킬 수 있었으며 이로 인해 다층박막의 두께를 증가시킬 수 있었다. 이러한 다층박막의 두께 증가를 통해 종이의 강도를 더욱 향상시킬 수 있었다. 동일한 층의 다층박막 형성 조건에서는 PDADMAC보다는 양성전분이 다층박막 최외각층에 존재할 때 종이의 강도 향상에 더욱 효과적이었다. 그러나 PDADMAC/PSS 조합도 0.1 M NaCl 조건에서 7 레이어까지 다층박막을 형성하면 양성전분/A-PAM 조합 3 레이어 조건과 유사한 수준의 강도 향상을 나타낼 수 있었다. 양성전분 조합의 다층박막은 주로 수소결합 생성을 통해 강도를 향상시킨 것으로 판단되며, PDADMAC 조합의 다층박막은 고분자전해질 사슬에 의한 interdifussion 현상, van der Waals 결합과 coulomb 결합 형성에 의해 강도를 향상시키는 것으로 판단되었다. 표면 형상이 상이한 무정형의 중질탄산칼슘, 침상형의 경질탄산칼슘, 판상형의 카올린 충전물에 각각 다층박막을 형성하였으며, 충전물 형상이 종이 강도에 미치는 영향을 구명하였다. 판상형의 카올린에 다층박막을 형성한 경우 가장 높은 강도 향상을 나타내어, 충전물 입자의 표면이 매끄러울수록 다층박막이 종이의 강도를 향상시키는 데에 더 효과적인 것으로 판단되었다.
PEM기술의 현장 적용 방안을 위해 세 대의 인라인 믹서와 펌프로 구성된 연속식의 무세척 다층박막 형성 시스템 (Inline washless PEM system)을 제안하였다. 본 시스템을 통해 제조한 개질 충전물 역시 종이 적용 시 높은 강도 향상을 나타내었다. 이러한 결과를 토대로 연속식의 무세척 다층박막 형성 시스템은 실제 제지 현장에 적용하기에 적합한 것으로 판단되었다.
PEM 기술의 폭 넓은 활용을 위한 방안으로 항균성 종이 제조 방안을 제시하고자 하였다. PVAm/PAA 다층박막이 형성된 카올린 입자를 내첨한 종이의 박테리아 제거 효율은 90% 미만으로 항균 특성을 나타내지 않았지만, 종이에 표면처리 할 경우 99% 이상의 박테리아 제거효율을 나타내어 우수한 항균 특성을 나타내었다. 이러한 항균 특성을 나타내는 개질 카올린은 종이의 강도 역시 향상시킬 수 있어, 종이의 강도 향상뿐만 아니라 종이에 항균성을 부여할 수 있는 것으로 여겨졌다.
본 연구를 통해 충전물에 대한 고분자전해질 다층박막 형성 특성을 이해하고, 다층박막이 충전지의 강도를 향상시키는 기작에 대해 구명할 수 있었다. 또한 고분자전해질 다층박막 형성 기술을 실제 산업으로 적용하기 위한 처리 방안과 고분자전해질 다층박막 형성 기술을 통해 종이에 항균성과 같은 기능성을 부여할 수 있는 가능성이 제시되었다.
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dc.description.abstractInorganic filler particles are one of the most important additives in papermaking industry, typically for printing and writing paper grades. Advantages of fillers are to improve optical properties, smoothness, printability of papers, and to save final cost and drying energy. To maximize the advantages of fillers, demand for the increase in filler content of paper, so-called high filler loading, has been increased. However, fillers give negative effect on strength of paper. High filler loading is mainly focused on minimization of the negative effect of fillers on paper strength. Polyelectrolytes multilayer (PEM) technique is regarded as one of the surface modification techniques to increase paper strength. Even though there are many researches about application of PEM technique into papermaking science, these previous researches are mostly focused on surface modification of pulp fibers and its effect on paper without fillers. In this study, therefore, possibility of PEM technique for high filler loading was investigated. Furthermore, applicable model of PEM process to papermaking industry and antibacterial paper with high strength using PEM fillers were proposed.
Firstly, strengthening effect of PEM treatment for highly filled paper was investigated. PEM treatment can be performed on either fibers or fillers. Two approaches gave strength improvement of filled paper. Even though PEM treatment on fibers improved strength of filled paper, this strengthening effect become weaker as filler content increased. However, PEM treatment on fillers was more effective for strength improvement of highly filled paper. This was because PEM treatment on fillers improved bonding strength between fiber and filler as well as bonding strength between fillers. This was confirmed by evaluation of specific debonding factor between fiber and filler, and measurement of breaking strength of dense film composed of fillers.
Factors affecting strength improvement of filled paper were investigated depending on characteristics of multilayer and morphological properties of fillers. The characteristics of multilayer were controlled by salt concentration during PEM treatment, and different types of polyelectrolytes. High salt concentration up to 0.1 M NaCl enabled to increase amounts of PDADMAC and PSS in multilayer onto GCC, and thickness of the multilayer, resulting in greater strengthening effect at given filler content. The multilayer with cationic starch showed greater strengthening effect than the multilayer with PDADMAC at given layer number, but PDADMAC /PSS 7 layers at 0.1 M NaCl gave similar strengthening effect with C-starch/A-PAM 3 layers. It was considered that strengthening mechanism was due to creation of additional hydrogen bonding in the case of multilayer with C-starch, and more interdiffusion of polymer chains and creation of van der Waals and coulombic bonding in the case of multilayer with PDADMAC. PEM treatment was performed onto three types of fillers, irregular type of GCC, scalenohedral type of PCC, and platy type of kaolin. PEM treatment on the platy type of kaolin provided the highest strengthening effect on filled paper. It was considered that the smoother surface of fillers showed the higher strengthening effect of multilayer on filled paper.
To suggest mill application model for PEM treatment on fillers, inline washless PEM system was designed for fast and continuous PEM treatment. The inline washless PEM system consisting of three inline mixers and pumps can form multilayer onto fillers up to 3 layers. Zeta potential and particle size of washless PEM fillers can be controlled by addition level of polyelectrolytes, and shear, respectively. The washless PEM fillers provided a little more effective for strength improvement of filled paper than conventional PEM fillers. Therefore, it was considered that this inline washless PEM system would be proper to apply to papermaking industry.
As one of the application of PEM technique in the papermaking, antibacterial paper using PEM treated fillers was proposed. PVAm is known to be one of the polyelectrolytes that shows antibacterial activity, thus PVAm/PAA multilayer was formed onto kaolin particles. Internal addition of the PEM kaolin to paper showed antibacterial activity less than 90%, and great strengthening effect on the filled paper. Surface treatment of the PEM kaolin on paper gave great antibacterial activity more than 99%. This PEM kaolin with antibacterial activity is expected to be used as strengthening fillers of filled paper as well as fabrication of antibacterial paper.
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dc.description.tableofcontentsChapter 1 Introduction 1
1. Introduction 2
2. Objectives 7

Chapter 2 Literature review 9
1. Influences of fillers on strength of paper 10
2. High filler loading techniques 12
3. Polyelectrolytes multilayering (PEM) 14
3.1 General aspects for PEM 14
3.2 PEM in the papermaking 18
3.3 PEM for high filler loading 20
4. Mechanism for strengthening effect of polyelectrolytes 21

Chapter 3 Investigation on strengthening effect of polyelectrolytes multilayer on filled paper 23
1. Introduction 24
2. Materials and methods 26
2.1 Materials 26
2.2 Formation of polyelectrolytes multilayer on filler particles 28
2.3 Formation of polyelectrolytes multilayer on pulp fiber 30
2.4 Properties of PEM GCC and PEM fiber 31
2.4.1 Zeta potential and particle size 31
2.4.2 Adsorbed amount of polyelectrolytes 31
2.5 Preparation and properties of filled handsheets 32
2.5.1 Handsheets preparation 32
2.5.2 Properties of filled handsheets 35
2.5.2.1 Structural properties 35
2.5.2.2 Mechanical properties 35
2.5.2.3 Optical properties 36
2.6 Bonding ability of PEM fillers 36
2.6.1 Measurement of bonding force between fibers and fillers 36
2.6.1.1 Preparation of model fibers sheets 37
2.6.1.2 Preparation of a filler layer between the model fibers sheets 37
2.6.1.3 Delamination test 39
2.6.2 Measurement of bonding strength between fillers 40
3. Results and discussion 41
3.1 Properties of PEM fibers and PEM GCC 41
3.2 Effect of PEM treatment on properties of filled handsheets 43
3.2.1 Influence of PEM treated fibers on paper properties 43
3.2.2 Physics properties of filled paper 45
3.2.3 Improvement on mechanical properties of filled paper 48
3.2.4 Optical properties of filled paper 59
3.3 Mechanism for improvement on strength of filled paper by PEM treatment 63
3.3.1 Determination of improvement on bonding strength between fibers-fillers 63
3.3.2 Bonding ability between PEM treated fillers 69
4. Summary 73
Chapter 4 Factors affecting properties of PEM fillers and strength of filled paper 75
1. Introduction 76
2. Materials and methods 79
2.1 Materials 79
2.2 Formation of polyelectrolytes multilayer on filler particles 82
2.3 Properties of PEM fillers 83
2.3.1 Zeta potential and particle size of PEM filler 83
2.3.2 Adsorbed amount of polyelectrolytes 83
2.3.3 Charge demand of PEM GCC 84
2.3.4 Monitoring of growth of PD/PSS multilayer using Quartz Crystal Microbalance with Dissipation 85
2.4 Preparation and properties of filled handsheets 86
2.4.1 Handsheets preparation 86
2.4.2 Properties of filled handsheets 88
2.5 Bonding ability of PEM fillers 89
2.5.1 Measurement of bonding force between fibers and fillers 89
2.5.2 Measurement of bonding strength between fillers 89
3. Results and discussion 90
3.1 Effect of multilayer characteristics on properties of PEM GCC and strength of filled paper 90
3.1.1 Effect on properties of PEM GCC depending on salt concentration 85
3.1.2 Effect on strength of filled paper 102
3.2 Effect of nature of polyelectrolytes on strength of filled paper 108
3.3 Effect of filler morphology on strength of filled paper 117
3.3.1 Properties of PEM fillers 117
3.3.2 Effect of types of fillers on handsheets properties 126
4. Summary 133
Chapter 5 Application of polyelectrolytes multilayering: washless polyelectrolytes multilayering for mill application and antibacterial effect of PEM fillers 135
1. Introduction 136
2. Materials and methods 139
2.1 Materials 139
2.1.1 Pulp fibers 139
2.1.2 Fillers 139
2.1.3 Polyelectrolytes 139
2.1.4 Bacteria 140
2.2 Washless polyelectrolytes multilayering 141
2.2.1 Inline washless polyelectrolytes multilayering 141
2.2.2 Handsheets preparation 142
2.2.3 Measurement 143
2.2.3.1 Properties of inline washless PEM GCC 143
2.2.3.2 Handsheets properties 144
2.3 Antibacterial PEM fillers 145
2.3.1 Formation of PVAm/PAA multilayer on kaolin 145
2.3.2 Preparation of antibacterial paper 146
2.3.3 Antibacterial test 147
2.3.4 Evaluation of cell membrane integrity after exposure onto antibacterial paper 149
3. Results and discussion 150
3.1 Inline washless polyelectrolytes multilayering 150
3.1.1 Investigation on treatment conditions for inline washless process 150
3.1.2 Effect of inline washless PEM GCC on strength of filled paper 161
3.2 Antibacterial effect of PEM fillers 166
3.2.1 Properties of PVAm/PAA kaolin and its effect on paper strength 166
3.2.2 Antibacterial effect 169
4. Summary 178

Chapter 6 Overall conclusions 180

References 186

초록 201
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dc.formatapplication/pdf-
dc.format.extent4107200 bytes-
dc.format.mediumapplication/pdf-
dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subjectPolyelectrolytes multilayering-
dc.subjectfillers-
dc.subjectfilled paper-
dc.subjectmechanical properties-
dc.subjectstrengthening mechanism-
dc.subjectwashless polyelectrolytes multilayering-
dc.subjectantibacterial activity-
dc.subject.ddc634-
dc.titlePolyelectrolytes Multilayering of Fillers for Strength Improvement of Filled Paper and Their Functionality-
dc.title.alternative충전지 강도 향상과 기능성 부여를 위한 충전물의 고분자전해질 다층 흡착 처리 기술-
dc.typeThesis-
dc.description.degreeDoctor-
dc.citation.pages203-
dc.contributor.affiliation농업생명과학대학 산림과학부-
dc.date.awarded2017-02-
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College of Agriculture and Life Sciences (농업생명과학대학)Dept. of Forest Sciences (산림과학부)Theses (Ph.D. / Sc.D._산림과학부)
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