innovative applications of regenerated wood cellulose...

Application of electro-hydrodynamic processing to coat paper and board – Use of nanocellulose as the coating filler for high performance papermaking products

COST Action FP1205 Innovative applications of regenerated wood cellulose fibres

Christian Kossel, Adriane Cherpinski and Jose M. Lagaron [email protected]

31.01.2017

2

Papiertechnische Stiftung, Munich, Germany Fibre-based solutions for successful innovations

Founders Facts

• VDP – German Pulp and Paper Association • HPV – German Employers‘ Association of the

Paper, Board and Plastics Converting Industry • FPT – Paper Technology Research Association

• Founded in 1951 • 100 employees • Munich and Heidenau/Dresden • Independent and neutral

31.01.2017

The PTS business units

Efficient paper manufacturing

Semi-finished products and biocomposites

Developing new markets

Coated barriers

Packaging with novel functions

Contact-free production processes

Functionalisation of web-shaped materials

Optimisation of printability and runnability

Surface assessment

Introduction of Industry 4.0 projects

Quality assurance solutions

Automation and measuring technology solutions

Testing services for paper and board

Handling of Complaints

Assessment of product performance

3

Fibres & Composites

Packaging & Conformity

Printing & funct. surfaces

Industry 4.0 Materials testing & Analytics

31.01.2017

IATA-CSIC, Valencia, Spain

The Instituto de Agroquímica y Tecnología de Alimentos (IATA) is a research centre that belongs to the Consejo Superior de Investigaciones Científicas and was founded in 1966

4

31.01.2017

IATA-CSIC, Valencia, Spain

IATA’s scientific and technological objective is to conduct excellent research about sustainable food production, food safety, food impact on health and consumer acceptance. The research focuses on areas:

• Food Chemistry and Biochemistry

• Microbiology and microorganism and enzyme engineering

• Biological activity of food components

• Novel materials and nanotechnology for food applications and food preservation processes as well as food sectors

• Cereals and related products

• Meat and meat products

• Fruit and fruit juices, wine, etc.

5

31.01.2017

Introduction

Global packaging market is witnessing fast growth. Nanotechnological applications are used in several segments – with packaging segment as the highest. Nanocellulose production in 2017: 1600t/a – 3500t/a with 14% market share in pulp and paper industry.

Advantages of electrospun nanocelluloses:

high surface area per unit mass

high aspect ratio (up to 1000)

high porosity (~90%)

lightweight, tuneable pore size

submicron to nanoscale diameter

high reactivity, barrier properties

Pajpai, 2016

Presentatör

Presentationsanteckningar

high surface area per unit mass (1-100g/m²)

31.01.2017

Introduction

Applications (excerpt):

Fibre reinforcement

Fiber based active packaging

Drug delivery

Nanosensors Intelligent Packaging

Active packaging systems include :

Oxygen scavengers, antimicrobial agents, moisture absorbers, antioxidants or flavor or odor absorbing systems.

In addition, food contact packaging materials are acceptable by customers if they are natural and non-toxic like bioactive plant extracts or natural compounds (GRAS status).

31.01.2017

E - Spinning technique

• Electrical potential (10– 50 kV) is applied

• Pendant drop becomes highly electrified resulting in the deformation of liquid drops Taylor cone

• Voltage reaching a critical value: the electrostatic repulsion forces prevail over the solution surface tension Jet ejection to collector

• The jet becomes thinner in air due to fibre elongation and solvent evaporation.

Flowrate V̇

Voltage [V]

Current [I]

dc

Charge density ∑=I/Q

Electric field E∞=V/dc

www.weistron.com

31.01.2017

Experimental

Two different types of PVOH were used – PVOH 18-88 and PVOH 28-88.

The concentration of PVOH was 12 wt/wt %, dissolved using a magnetic stirrer at 75°C for 24h.

The viscosity, surface tension and the conductivity were measured

Nanocrystals of cellulose (CNCs) were added in 1 wt/wt %

An additional PHB layer was coated on the top. The concentration of PHB in the solution was 10 wt/wt%.

About 24 different samples were produced

31.01.2017

Experimental

31.01.2017

Experimental

The experiments were performed on a FLUIDNATEK LE-10 electrospinning tool designed for product development

www.bioinicia.com

31.01.2017

Experimental

The selected conditions generated a homogeneous electrospun nanofiber film

Parameters LE-10 PVOH V̇ [ml/h] 0.5 dsyringe [mm] 22.5 V [kV] 18 rpmcollector 200 dc [mm] 150

31.01.2017

Experimental

Thermal post-processing of the electrospun films were carried out to improve fiber cohesion

Advantages:

Enhance adhesion

Improve membrane compactness (eliminate 'fluffiness' or stray fibers)

Improve mechanical and barrier properties

tPTT

31.01.2017

Results - SEM analysis

SEM was used to analyse the structure and the morphology of the electrospun nanofibers

SEM images of electrospun fibers with a magnification between 2k and 30k The nanofiber diameter ranged between 145 -190 nm

31.01.2017

Results – Dependence of porosity

SEM analysis of fiberfilms after post-processing

Porosity depended on annealing time

tPTT

31.01.2017

Results: multi-layer electrospun nanofiber

After settings the parameters for PVOH – CNC solutions, PHB was added as secondary layer on top

The paper itself had a grammage of 120g/m² and an A4 shape

31.01.2017

Results

- Grease resistance KIT-Test according to TAPPI T559

- Water absorptiveness according to Cobb-Test (ISO 535)

- Surface tension / polarity of surfaces and contact angle according to PTS-PP:103/85

- Foldability and scoring characteristics according to DIN 55 437-2

- Roughness/permeability meter according to Bendtsen (ISO 8791-2 )

31.01.2017

Characterization

Method Non coated E-Spin coated outcome thickness [µm] 160.5 170 ~ 10µm layer Grease resistance

KIT- Test TAPPI T559

<1 >12 high resistance

Water absorptiveness

[g/m²] Cobb-Test

29.2 0.85 low water absorption

Surface tension [mN/m] 21.5 39.4 wettability Contact angle [°] PTS-

PP:103/85 H2O: 109.9 H2O: 68.3 <90° +

>90° - Formamide: 89.1 Formamide: 57.0 Foldability and scoring characteristics

[µm] DIN 55437-2

CD: 7.1 MD: 6.7

CD: 7.2 MD: 4.8

No influence of the coating

Roughness meter [ml/min] Bendtsen

504.4 64.4 <100ml/min ~ Smooth

Presentatör

Presentationsanteckningar

The Kit Test (Tappi T559) The Kit test measures the degree of repellence or anti-wicking of paper and boards which have been treated with fluorochemical sizing agents used to prevent wetting of the cellulose fibres of the material. Test solutions with varying strengths of castor oil, toluene, heptane and turpentine are used. The highest numbered solution (the most aggressive) that remains on the surface of the paper without causing failure is reported as the "kit rating" (maximum 12). Kit rating highest number for a series of test solutions that can be placed on the surface of the paper or board without causing a wetting interaction by darkening the paper or board surface Surface tension: = Characteristic variable to determine the wetability respectively the adhesion of coatings ST of the liquid should be smaller than ST of surface Better wetability Paper standard ~ 40-50mN/m Hydrophobic layer: ~20-25mN/m ST of liquid is higher less wetability <-> Hydrophobic properties ST derived out of the Young equation measured via FIBRO Contact angle measurement device Why Formamide and H20 Surfacte tension is smiliar, but polarity is different Roughness meter according to Bendtsen: Air is flows between a reference surface (metalring) and the paper surface, Unit [ml/min] >200ml/min ~ Rough <100ml/min ~ smooth �Water absorptiveness according to COBB: Water absorptiveness is a function of various characteristics of paper and board such as sizing, porosity, etc.. Water absorptiveness: The mass of water absorbed in a sepcific time by 1m² under 1cm under water

31.01.2017

Results





[g/m²] Cobb-Test



PP:103/85 H2O: 109.9 H2O: 68.3 <90° +


[µm] DIN 55437-2

CD: 7.1 MD: 6.7

CD: 7.2 MD: 4.8



504.4 64.4 <100ml/min ~ Smooth

31.01.2017

Results





Cobb-Test ISO 535



PP:103/85 H2O: 109.9 H2O: 68.3 <90° +


[µm] DIN 55437-2

CD: 7.1 MD: 6.7

CD: 7.2 MD: 4.8



504.4 64.4 <100ml/min ~ Smooth

31.01.2017

Results





[g/m²] Cobb-Test



PP:103/85 H2O: 109.9 H2O: 68.3 <90° +


[µm] DIN 55437-2

CD: 7.1 MD: 6.7

CD: 7.2 MD: 4.8



504.4 64.4 <100ml/min ~ Smooth

31.01.2017

Results from CSIC

Method Parameter DSC thermal properties

(degree of crystallization) WVTR barrier properties Aroma barrier (Limonene)

barrier properties

SEM fiber diameter and morphology

31.01.2017

26

SEM Paper PVOH PHB - Ptt

31.01.2017

SEM Paper PVOH / fibers PVOH NonPtt

28

31.01.2017

Water Vapor Permeability

30

0

5

10

15

20

25

30

35

Uncoated paper Film PVOH 1% ncn Mundi PVOH PHB 1% ncn Film PHB PVOH PHB 1% ncn

34

9,6

4,5

0,3

Wat

er V

apor

Per

mea

bilit

y x

10-1

4 (kg

·m-1

·Pa−

1 s−

1)

31.01.2017

Limonene Permeability

31

0

5

10

15

20

25

30

Uncoated paper Film PVOH 1% ncn Mundi PVOH PHB 1% ncn Film PHB PVOH PHB 1% ncn

28

6,8 5,9

0,4

Lem

onen

Per

mea

bilit

y x

10-1

4 (kg

·m-1

·Pa−

1 s−

1)

31.01.2017

Conclusions and further work

To achieve good results the machine parameters (V̇, V, rpm, tip-to collector-distance, tspinning) as well as the material parameters (viscosity, concentration, MW, surface tension and conductivity) had to be optimized

The results suggest that the use of nanocellulose as a filler in combination with PVOH shows great potential to produce fully biobased paper with potentially enhanced properties

31.01.2017

Thank you for your attention

Christian Kossel Tel +49 89 / 12146-597 [email protected]

innovative applications of regenerated wood cellulose...

Documents